U.S. patent application number 14/939583 was filed with the patent office on 2016-03-10 for polymeric blends and related optoelectronic devices.
The applicant listed for this patent is RAYNERGY TEK INC.. Invention is credited to Zhihua Chen, Martin Drees, Antonio Facchetti, Shaofeng Lu, Hualong Pan.
Application Number | 20160072070 14/939583 |
Document ID | / |
Family ID | 49210634 |
Filed Date | 2016-03-10 |
United States Patent
Application |
20160072070 |
Kind Code |
A1 |
Drees; Martin ; et
al. |
March 10, 2016 |
POLYMERIC BLENDS AND RELATED OPTOELECTRONIC DEVICES
Abstract
The present invention relates to all-polymer blends including an
electron-acceptor polymer and an electron-donor polymer, capable of
providing improved device performance, for example, as measured by
power conversion efficiency, when used in photovoltaic cells.
Inventors: |
Drees; Martin; (Glenview,
IL) ; Pan; Hualong; (Skokie, IL) ; Chen;
Zhihua; (Skokie, IL) ; Lu; Shaofeng; (Skokie,
IL) ; Facchetti; Antonio; (Chicago, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
RAYNERGY TEK INC. |
HSINCHU |
|
TW |
|
|
Family ID: |
49210634 |
Appl. No.: |
14/939583 |
Filed: |
November 12, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14617508 |
Feb 9, 2015 |
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14939583 |
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13844660 |
Mar 15, 2013 |
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14617508 |
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61614302 |
Mar 22, 2012 |
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61724140 |
Nov 8, 2012 |
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61733404 |
Dec 4, 2012 |
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61733406 |
Dec 4, 2012 |
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Current U.S.
Class: |
136/263 |
Current CPC
Class: |
H01L 51/0035 20130101;
C08G 73/1064 20130101; H01L 51/4253 20130101; Y02E 10/549 20130101;
H01L 51/0036 20130101; H01L 31/0256 20130101; H01L 51/0043
20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00 |
Claims
1. An optoelectronic device comprising a first electrode, a second
electrode, and a photoactive layer disposed between the first and
second electrodes, the photoactive layer comprising a
polymer-polymer blend semiconductor material, the polymer-polymer
blend semiconductor material comprising an electron-donor polymer
and an electron-acceptor polymer, wherein: the electron-acceptor
polymer is represented by Formula 1: ##STR00093## wherein: .pi.-1
is ##STR00094## R.sup.1 is selected from the group consisting of a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, a C.sub.1-30
haloalkyl group, a C.sub.6-20 aryl group and a 5-14 membered
heteroaryl group, wherein the C.sub.6-20 aryl group and the 5-14
membered heteroaryl group optionally are substituted with a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, or a C.sub.1-30
haloalkyl group; M.sup.a is a repeat unit comprising one or more
conjugated moieties that does not include a rylene diimide; and n
is an integer in the range of 2 to 5,000; and the electron-donor
polymer has an alternating push-pull structure represented by: *
D-A *, wherein: the donor subunit (D) comprises a benzodithiophene
moiety selected from the group consisting of: ##STR00095##
##STR00096## is selected from the group consisting of: ##STR00097##
each of which optionally is substituted with 1-2 R.sup.b groups,
and R.sup.b, at each occurrence, independently is a C.sub.3-40
alkyl group or branched alkyl group; and the acceptor subunit (A)
is represented by the following moiety: ##STR00098## wherein
R.sup.c, at each occurrence, is H or a C.sub.6-20 alkyl group;
R.sup.f, at each occurrence, independently is selected from H, F,
Cl, C(O)R.sup.e, C(O)OR.sup.e, and S(O).sub.2R.sup.e; where
R.sup.e, at each occurrence, independently is a linear or branched
C.sub.6-20 alkyl group; r is 0 or 1.
2. The device of claim 1, wherein the electron-acceptor polymer is
represented by Formula 3: ##STR00099## wherein: R' is selected from
the group consisting of H, F, Cl, --CN, and -L-R, wherein L, at
each occurrence, independently is selected from the group
consisting of --O--, --S--, --C(O), --C(O)O--, and a covalent bond;
and R, at each occurrence, independently is selected from the group
consisting of a C.sub.6-20 alkyl group, a C.sub.6-20 alkenyl group,
and a C.sub.6-20 haloalkyl group; m is 1, 2, 3, 4, 5 or 6.
3. The device of claim 1, wherein the electron-acceptor polymer is
represented by Formula 6: ##STR00100##
4. The device of claim 1, wherein R.sup.1 is selected from the
group consisting of a branched C.sub.3-20 alkyl group, a branched
C.sub.4-20 alkenyl group, and a branched C.sub.3-20 haloalkyl
group.
5. The device of claim 4, wherein R.sup.1 is selected from the
group consisting of: ##STR00101##
6. The device of claim 1, wherein the electron donor polymer is an
alternating copolymer selected from the group consisting of:
##STR00102## ##STR00103## wherein R.sup.b, at each occurrence, is a
linear or branched C.sub.3-40 alkyl group; R.sup.c, at each
occurrence, is H or a C.sub.6-20 alkyl group; and n is an integer
in the range of 5 to 5,000.
7. The device of claim 1, wherein the electron donor polymer is a
random copolymer selected from the group consisting of:
##STR00104## ##STR00105## ##STR00106## wherein R.sup.b, at each
occurrence, is a linear or branched C.sub.3-40 alkyl group; R, at
each occurrence, is a C.sub.6-20 alkyl group; x and y independently
are a real number, wherein 0.1.ltoreq.x.ltoreq.0.9,
0.1.ltoreq.y.ltoreq.0.9 (0.2.ltoreq.x.ltoreq.0.8,
0.2.ltoreq.y.ltoreq.0.8), and the sum of x and y is about 1; and n
is an integer in the range of 5 to 5,000.
8. The device of claim 1 configured as an organic photovoltaic
device comprising an anode, a cathode, optionally one or more anode
interlayers, optionally one or more cathode interlayers, and in
between the anode and the cathode the photoactive layer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 14/617,508, filed on Feb. 9, 2015, which is a
continuation of U.S. patent application Ser. No. 13/844,660, filed
on Mar. 15, 2013, which claims priority to and the benefit of U.S.
Provisional Patent Application Ser. No. 61/614,302, filed on Mar.
22, 2012, U.S. Provisional Patent Application Ser. No. 61/724,140,
filed on Nov. 8, 2012, U.S. Provisional Patent Application Ser. No.
61/733,404, filed on Dec. 4, 2012, and U.S. Provisional Patent
Application Ser. No. 61/733,406, filed on Dec. 4, 2012, the
disclosure of each of which is incorporated by reference herein in
its entirety.
BACKGROUND
[0002] Organic photovoltaics (OPVs) have seen significant progress
over the last few years. A key milestone in this field has been the
development of bulk heterojunction (BHJ) blends as the photoactive
layer. In a BHJ solar cell, an electron donor (hole-transporting,
p-type) semiconductor material and an electron acceptor
(electron-transporting, n-type) semiconductor material typically
are blended in solution. The mixture then is cast via
solution-phase techniques onto one of the electrodes (e.g., a high
work function indium tin oxide functioning as the transparent
anode), with the donor and acceptor phases separating during the
solvent drying process to form the BHJ photoactive layer, which has
the morphology of a bicontinuous interpenetrating network. A low
work function metal such as Al or Ca usually is deposited as the
top layer which functions as the cathode. FIG. 1 illustrates a
representative structure of an OPV cell. Due to dramatically
improved donor-acceptor interfacial area, OPV cells based upon BHJ
blends usually have much better performance than planar bilayer
structures.
[0003] While designing novel materials is critical to continued
improvements in OPV device performance, recent research has been
focused mainly on the development of new conjugated polymers as
donor materials, with soluble molecular fullerene derivatives such
as [6,6]-phenyl-C.sub.61-butyric acid methyl ester (C60PCBM or
PCBM) and [6,6]-phenyl-C.sub.71-butyric acid methyl ester (C70PCBM)
remaining the dominant acceptors. Although fullerene derivatives
show excellent charge separation behavior with a wide variety of
donor materials and good electron transport, their absorption in
the visible and NIR region is limited. In addition, their lowest
unoccupied molecular orbital (LUMO) energy level, the governing
property for the open circuit voltage (V.sub.oc) of OPVs, is fixed
and cannot be easily adjusted. Therefore, the two major loss
mechanisms in today's OPVs are the low photocurrent (J.sub.sc) due
to insufficient photon absorption and the low V.sub.oc compared to
the band gap of the absorbers due to non-optimum LUMO-LUMO offset
of donor and acceptor materials. In addition, in terms of
processing, the use of an acceptor polymer (instead of a molecular
acceptor like a fullerene derivative) with a donor polymer will
allow more uniform films to form over large areas, hence
facilitating large-scale production of OPV modules.
[0004] Efforts to replace fullerene derivatives with other organic
acceptor materials have not been very successful to date.
Particularly, the approach of using n-type polymers as acceptors in
OPVs has not yielded high power conversion efficiencies (PCEs) even
though a range of materials with good electron transporting
properties and good absorption in the visible and NIR are
available. Particularly, one of the observations is that
electron-transporting or n-type polymeric semiconductors that show
high performance in thin film transistor (TFT) applications do not
excel necessarily as OPV acceptors. See Anthony et al., "N-Type
Organic Semiconductors in Organic Electronics," Adv. Mater., vol.
22, no. 34, pp. 3876-3892 (2010). To date, no PCE over 3% has been
reported for all-polymer, fullerene-free OPVs.
[0005] For example, different groups have investigated OPVs based
upon the combination of poly(3-hexylthiophene), P3HT, as the donor
material and
poly([N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-
-diyl]-alt-5,5'-(2,2'-bithiophene)), P(NDI2OD-T2), as the acceptor
material. First studies yielded very low PCEs of 0.2%. See Moore et
al., "Polymer Blend Solar Cells Based on a High-Mobility
Naphthalenediimide-Based Polymer Acceptor: Device Physics,
Photophysics and Morphology," Adv. Energy Mater., vol. 1, no. 2,
pp. 230-240. Significant improvements in PCE to 0.6% were achieved
through improved processing solvent, and then to 1.4% by
controlling the aggregation of P(NDI2OD-T2) through solvent
mixtures and hot solvent processing. See Fabiano et al., "Role of
Photoactive Layer Morphology in High Fill Factor All-Polymer Bulk
Heterojunction Solar Cells," J. Mater. Chem., vol. 21, no. 16, pp.
5891-5896; and Schubert et al., "Influence of Aggregation on the
Performance of All-Polymer Solar Cells Containing Low-Bandgap
Naphthalenediimide Copolymers," Adv. Energy. Mater., vol. 2, no. 3,
pp. 369-380.
[0006] Accordingly, the art desires new polymeric blends that can
enable high-efficiency all-polymer OPV devices.
SUMMARY
[0007] In light of the foregoing, the present teachings relate to
polymeric blends that include an electron-donor polymer and an
electron-acceptor polymer, where such polymeric blends can yield
unexpectedly high power conversion efficiencies in OPV devices when
compared to prior art polymeric blends.
[0008] The foregoing as well as other features and advantages of
the present teachings will be more fully understood from the
following figures, description, examples, and claims.
BRIEF DESCRIPTION OF DRAWINGS
[0009] It should be understood that the drawings described below
are for illustration purposes only. The drawings are not
necessarily to scale, with emphasis generally being placed upon
illustrating the principles of the present teachings. The drawings
are not intended to limit the scope of the present teachings in any
way.
[0010] FIG. 1 illustrates a representative organic photovoltaic
device (also known as a solar cell) structure, which can
incorporate the present polymeric blends as the photoactive
layer.
DETAILED DESCRIPTION
[0011] Throughout the application, where compositions are described
as having, including, or comprising specific components, or where
processes are described as having, including, or comprising
specific process steps, it is contemplated that compositions of the
present teachings also consist essentially of, or consist of, the
recited components, and that the processes of the present teachings
also consist essentially of, or consist of, the recited process
steps.
[0012] In the application, where an element or component is said to
be included in and/or selected from a list of recited elements or
components, it should be understood that the element or component
can be any one of the recited elements or components, or the
element or component can be selected from a group consisting of two
or more of the recited elements or components. Further, it should
be understood that elements and/or features of a composition, an
apparatus, or a method described herein can be combined in a
variety of ways without departing from the spirit and scope of the
present teachings, whether explicit or implicit herein.
[0013] The use of the terms "include," "includes", "including,"
"have," "has," or "having" should be generally understood as
open-ended and non-limiting unless specifically stated
otherwise.
[0014] The use of the singular herein includes the plural (and vice
versa) unless specifically stated otherwise. In addition, where the
use of the term "about" is before a quantitative value, the present
teachings also include the specific quantitative value itself,
unless specifically stated otherwise. As used herein, the term
"about" refers to a .+-.10% variation from the nominal value unless
otherwise indicated or inferred.
[0015] It should be understood that the order of steps or order for
performing certain actions is immaterial so long as the present
teachings remain operable. Moreover, two or more steps or actions
may be conducted simultaneously.
[0016] As used herein, a component (such as a thin film layer) can
be considered "photoactive" if it contains one or more compounds
that can absorb photons to produce excitons for the generation of a
photocurrent.
[0017] As used herein, fill factor (FF) is the ratio (given as a
percentage) of the actual maximum obtainable power, (P.sub.m or
V.sub.mp*J.sub.mp), to the theoretical (not actually obtainable)
power, (J.sub.sc*V.sub.oc). Accordingly, FF can be determined using
the equation:
FF=(V.sub.mp*J.sub.mp)/(J.sub.sc*V.sub.oc)
where J.sub.mp and V.sub.mp represent the current density and
voltage at the maximum power point (P.sub.m), respectively, this
point being obtained by varying the resistance in the circuit until
J*V is at its greatest value; and J.sub.sc and V.sub.oc represent
the short circuit current and the open circuit voltage,
respectively. Fill factor is a key parameter in evaluating the
performance of solar cells. Commercial solar cells typically have a
fill factor of about 0.60% or greater.
[0018] As used herein, the open-circuit voltage (V.sub.oc) is the
difference in the electrical potentials between the anode and the
cathode of a device when there is no external load connected.
[0019] As used herein, the power conversion efficiency (PCE) of a
solar cell is the percentage of power converted from incident light
to electrical energy. The PCE of a solar cell can be calculated by
dividing the maximum power point (P.sub.m) by the input light
irradiance (E, in W/m.sup.2) under standard test conditions (STC)
and the surface area of the solar cell (A, in m.sup.2). STC
typically refers to a temperature of 25.degree. C. and an
irradiance of 1000 W/m.sup.2 with an air mass 1.5 (AM 1.5)
spectrum.
[0020] As used herein, a "polymeric compound" (or "polymer") refers
to a molecule including a plurality of one or more repeating units
connected by covalent chemical bonds. A polymeric compound can be
represented by the general formula:
* M *
wherein M is the repeating unit or monomer. The polymeric compound
can have only one type of repeating unit as well as two or more
types of different repeating units. When a polymeric compound has
only one type of repeating unit, it can be referred to as a
homopolymer. When a polymeric compound has two or more types of
different repeating units, the term "copolymer" or "copolymeric
compound" can be used instead. For example, a copolymeric compound
can include repeating units
* M.sup.a * and * M.sup.b *,
where M.sup.a and M.sup.b represent two different repeating units.
Unless specified otherwise, the assembly of the repeating units in
the copolymer can be head-to-tail, head-to-head, or tail-to-tail.
In addition, unless specified otherwise, the copolymer can be a
random copolymer, an alternating copolymer, or a block copolymer.
For example, the general formula:
* M.sup.a.sub.x-M.sup.b.sub.y *
can be used to represent a copolymer of M.sup.a and M.sup.b having
x mole fraction of M.sup.a and y mole fraction of M.sup.b in the
copolymer, where the manner in which comonomers M.sup.a and M.sup.b
is repeated can be alternating, random, regiorandom, regioregular,
or in blocks. In addition to its composition, a polymeric compound
can be further characterized by its degree of polymerization (n)
and molar mass (e.g., number average molecular weight (M.sub.n)
and/or weight average molecular weight (M.sub.w) depending on the
measuring technique(s)).
[0021] As used herein, "solution-processable" refers to compounds
(e.g., polymers), materials, or compositions that can be used in
various solution-phase processes including spin-coating, printing
(e.g., inkjet printing, gravure printing, offset printing and the
like), spray coating, electrospray coating, drop casting, dip
coating, and blade coating.
[0022] As used herein, "halo" or "halogen" refers to fluoro,
chloro, bromo, and iodo.
[0023] As used herein, "oxo" refers to a double-bonded oxygen
(i.e., .dbd.O).
[0024] As used herein, "alkyl" refers to a straight-chain or
branched saturated hydrocarbon group. Examples of alkyl groups
include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and
iso-propyl), butyl (e.g., n-butyl, iso-butyl, sec-butyl,
tert-butyl), pentyl groups (e.g., n-pentyl, iso-pentyl,
neo-pentyl), hexyl groups, and the like. In various embodiments, an
alkyl group can have 1 to 40 carbon atoms (i.e., C.sub.1-40 alkyl
group), for example, 1-20 carbon atoms (i.e., C.sub.1-20 alkyl
group). In some embodiments, an alkyl group can have 1 to 6 carbon
atoms, and can be referred to as a "lower alkyl group." Examples of
lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl
and iso-propyl), and butyl groups (e.g., n-butyl, iso-butyl,
sec-butyl, ten-butyl). In some embodiments, alkyl groups can be
substituted as described herein. An alkyl group is generally not
substituted with another alkyl group, an alkenyl group, or an
alkynyl group.
[0025] As used herein, "haloalkyl" refers to an alkyl group having
one or more halogen substituents. At various embodiments, a
haloalkyl group can have 1 to 40 carbon atoms (i.e., C.sub.1-40
haloalkyl group), for example, 1 to 20 carbon atoms (i.e.,
C.sub.1-20 haloalkyl group). Examples of haloalkyl groups include
CF.sub.3, C.sub.2F.sub.5, CHF.sub.2, CH.sub.2F, CCl.sub.3,
CHCl.sub.2, CH.sub.2Cl, C.sub.2Cl.sub.5, and the like. Perhaloalkyl
groups, i.e., alkyl groups where all of the hydrogen atoms are
replaced with halogen atoms (e.g., CF.sub.3 and C.sub.2F.sub.5),
are included within the definition of "haloalkyl." For example, a
C.sub.1-40 haloalkyl group can have the formula
C.sub.sH.sub.2s+1-tX.sup.0.sub.t, where X.sup.0, at each
occurrence, is F, Cl, Br or I, s is an integer in the range of 1 to
40, and t is an integer in the range of 1 to 81, provided that t is
less than or equal to 2s+1. Haloalkyl groups that are not
perhaloalkyl groups can be substituted as described herein.
[0026] As used herein, "alkoxy" refers to --O-alkyl group. Examples
of alkoxy groups include, but are not limited to, methoxy, ethoxy,
propoxy (e.g., n-propoxy and isopropoxy), t-butoxy, pentoxyl,
hexoxyl groups, and the like. The alkyl group in the --O-alkyl
group can be substituted as described herein.
[0027] As used herein, "alkylthio" refers to an --S-alkyl group.
Examples of alkylthio groups include, but are not limited to,
methylthio, ethylthio, propylthio (e.g., n-propylthio and
isopropylthio), t-butylthio, pentylthio, hexylthio groups, and the
like. The alkyl group in the --S-alkyl group can be substituted as
described herein.
[0028] As used herein, "alkenyl" refers to a straight-chain or
branched alkyl group having one or more carbon-carbon double bonds.
Examples of alkenyl groups include ethenyl, propenyl, butenyl,
pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl groups, and
the like. The one or more carbon-carbon double bonds can be
internal (such as in 2-butene) or terminal (such as in 1-butene).
In various embodiments, an alkenyl group can have 2 to 40 carbon
atoms (i.e., C.sub.2-40 alkenyl group), for example, 2 to 20 carbon
atoms (i.e., C.sub.2-20 alkenyl group). In some embodiments,
alkenyl groups can be substituted as described herein. An alkenyl
group is generally not substituted with another alkenyl group, an
alkyl group, or an alkynyl group.
[0029] As used herein, "alkynyl" refers to a straight-chain or
branched alkyl group having one or more triple carbon-carbon bonds.
Examples of alkynyl groups include ethynyl, propynyl, butynyl,
pentynyl, hexynyl, and the like. The one or more triple
carbon-carbon bonds can be internal (such as in 2-butyne) or
terminal (such as in 1-butyne). In various embodiments, an alkynyl
group can have 2 to 40 carbon atoms (i.e., C.sub.2-40 alkynyl
group), for example, 2 to 20 carbon atoms (i.e., C.sub.2-20 alkynyl
group). In some embodiments, alkynyl groups can be substituted as
described herein. An alkynyl group is generally not substituted
with another alkynyl group, an alkyl group, or an alkenyl
group.
[0030] As used herein, a "cyclic moiety" can include one or more
(e.g., 1-6) carbocyclic or heterocyclic rings. The cyclic moiety
can be a cycloalkyl group, a heterocycloalkyl group, an aryl group,
or a heteroaryl group (i.e., can include only saturated bonds, or
can include one or more unsaturated bonds regardless of
aromaticity), each including, for example, 3-24 ring atoms and
optionally can be substituted as described herein. In embodiments
where the cyclic moiety is a "monocyclic moiety," the "monocyclic
moiety" can include a 3-14 membered aromatic or non-aromatic,
carbocyclic or heterocyclic ring. A monocyclic moiety can include,
for example, a phenyl group or a 5- or 6-membered heteroaryl group,
each of which optionally can be substituted as described herein. In
embodiments where the cyclic moiety is a "polycyclic moiety," the
"polycyclic moiety" can include two or more rings fused to each
other (i.e., sharing a common bond) and/or connected to each other
via a spiro atom, or one or more bridged atoms. A polycyclic moiety
can include an 8-24 membered aromatic or non-aromatic, carbocyclic
or heterocyclic ring, such as a C.sub.8-24 aryl group or an 8-24
membered heteroaryl group, each of which optionally can be
substituted as described herein.
[0031] As used herein, a "fused ring" or a "fused ring moiety"
refers to a polycyclic ring system having at least two rings where
at least one of the rings is aromatic and such aromatic ring
(carbocyclic or heterocyclic) has a bond in common with at least
one other ring that can be aromatic or non-aromatic, and
carbocyclic or heterocyclic. These polycyclic ring systems can be
highly .pi.-conjugated and optionally substituted as described
herein.
[0032] As used herein, "cycloalkyl" refers to a non-aromatic
carbocyclic group including cyclized alkyl, alkenyl, and alkynyl
groups. In various embodiments, a cycloalkyl group can have 3 to 24
carbon atoms, for example, 3 to 20 carbon atoms (e.g., C.sub.3-14
cycloalkyl group). A cycloalkyl group can be monocyclic (e.g.,
cyclohexyl) or polycyclic (e.g., containing fused, bridged, and/or
spiro ring systems), where the carbon atoms are located inside or
outside of the ring system. Any suitable ring position of the
cycloalkyl group can be covalently linked to the defined chemical
structure. Examples of cycloalkyl groups include cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl,
cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl,
norpinyl, norcaryl, adamantyl, and spiro[4.5]decanyl groups, as
well as their homologs, isomers, and the like. In some embodiments,
cycloalkyl groups can be substituted as described herein.
[0033] As used herein, "heteroatom" refers to an atom of any
element other than carbon or hydrogen and includes, for example,
nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium.
[0034] As used herein, "cycloheteroalkyl" refers to a non-aromatic
cycloalkyl group that contains at least one ring heteroatom
selected from O, S, Se, N, P, and Si (e.g., O, S, and N), and
optionally contains one or more double or triple bonds. A
cycloheteroalkyl group can have 3 to 24 ring atoms, for example, 3
to 20 ring atoms (e.g., 3-14 membered cycloheteroalkyl group). One
or more N, P, S, or Se atoms (e.g., N or S) in a cycloheteroalkyl
ring may be oxidized (e.g., morpholine N-oxide, thiomorpholine
S-oxide, thiomorpholine S,S-dioxide). In some embodiments, nitrogen
or phosphorus atoms of cycloheteroalkyl groups can bear a
substituent, for example, a hydrogen atom, an alkyl group, or other
substituents as described herein. Cycloheteroalkyl groups can also
contain one or more oxo groups, such as oxopiperidyl,
oxooxazolidyl, dioxo-(1H,3H)-pyrimidyl, oxo-2(1H)-pyridyl, and the
like. Examples of cycloheteroalkyl groups include, among others,
morpholinyl, thiomorpholinyl, pyranyl, imidazolidinyl,
imidazolinyl, oxazolidinyl, pyrazolidinyl, pyrazolinyl,
pyrrolidinyl, pyrrolinyl, tetrahydrofuranyl, tetrahydrothiophenyl,
piperidinyl, piperazinyl, and the like. In some embodiments,
cycloheteroalkyl groups can be substituted as described herein.
[0035] As used herein, "aryl" refers to an aromatic monocyclic
hydrocarbon ring system or a polycyclic ring system in which two or
more aromatic hydrocarbon rings are fused (i.e., having a bond in
common with) together or at least one aromatic monocyclic
hydrocarbon ring is fused to one or more cycloalkyl and/or
cycloheteroalkyl rings. An aryl group can have 6 to 24 carbon atoms
in its ring system (e.g., C.sub.6-20 aryl group), which can include
multiple fused rings. In some embodiments, a polycyclic aryl group
can have 8 to 24 carbon atoms. Any suitable ring position of the
aryl group can be covalently linked to the defined chemical
structure. Examples of aryl groups having only aromatic carbocyclic
ring(s) include phenyl, 1-naphthyl (bicyclic), 2-naphthyl
(bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic),
pentacenyl (pentacyclic), and like groups. Examples of polycyclic
ring systems in which at least one aromatic carbocyclic ring is
fused to one or more cycloalkyl and/or cycloheteroalkyl rings
include, among others, benzo derivatives of cyclopentane (i.e., an
indanyl group, which is a 5,6-bicyclic cycloalkyl/aromatic ring
system), cyclohexane (i.e., a tetrahydronaphthyl group, which is a
6,6-bicyclic cycloalkyl/aromatic ring system), imidazoline (i.e., a
benzimidazolinyl group, which is a 5,6-bicyclic
cycloheteroalkyl/aromatic ring system), and pyran (i.e., a
chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic
ring system). Other examples of aryl groups include benzodioxanyl,
benzodioxolyl, chromanyl, indolinyl groups, and the like. In some
embodiments, aryl groups can be substituted as described herein. In
some embodiments, an aryl group can have one or more halogen
substituents, and can be referred to as a "haloaryl" group.
Perhaloaryl groups, i.e., aryl groups where all of the hydrogen
atoms are replaced with halogen atoms (e.g., C.sub.6F.sub.5), are
included within the definition of "haloaryl." In certain
embodiments, an aryl group is substituted with another aryl group
and can be referred to as a biaryl group. Each of the aryl groups
in the biaryl group can be substituted as disclosed herein.
[0036] As used herein, "arylalkyl" refers to an -alkyl-aryl group,
where the arylalkyl group is covalently linked to the defined
chemical structure via the alkyl group. An arylalkyl group is
within the definition of a --Y--C.sub.6-14 aryl group, where Y is
as defined herein. An example of an arylalkyl group is a benzyl
group (--CH.sub.2--C.sub.6H.sub.5). An arylalkyl group can be
optionally substituted, i.e., the aryl group and/or the alkyl
group, can be substituted as disclosed herein.
[0037] As used herein, "heteroaryl" refers to an aromatic
monocyclic ring system containing at least one ring heteroatom
selected from oxygen (O), nitrogen (N), sulfur (S), silicon (Si),
and selenium (Se) or a polycyclic ring system where at least one of
the rings present in the ring system is aromatic and contains at
least one ring heteroatom. Polycyclic heteroaryl groups include
those having two or more heteroaryl rings fused together, as well
as those having at least one monocyclic heteroaryl ring fused to
one or more aromatic carbocyclic rings, non-aromatic carbocyclic
rings, and/or non-aromatic cycloheteroalkyl rings. A heteroaryl
group, as a whole, can have, for example, 5 to 24 ring atoms and
contain 1-5 ring heteroatoms (i.e., 5-20 membered heteroaryl
group). The heteroaryl group can be attached to the defined
chemical structure at any heteroatom or carbon atom that results in
a stable structure. Generally, heteroaryl rings do not contain
O--O, S--S, or S--O bonds. However, one or more N or S atoms in a
heteroaryl group can be oxidized (e.g., pyridine N-oxide, thiophene
S-oxide, thiophene S,S-dioxide). Examples of heteroaryl groups
include, for example, the 5- or 6-membered monocyclic and 5-6
bicyclic ring systems shown below:
##STR00001##
where T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (e.g.,
N-benzyl), SiH.sub.2, SiH(alkyl), Si(alkyl).sub.2, SiH(arylalkyl),
Si(arylalkyl).sub.2, or Si(alkyl)(arylalkyl). Examples of such
heteroaryl rings include pyrrolyl, furyl, thienyl, pyridyl,
pyrimidyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl,
pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl,
isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuryl,
benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl,
quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl,
benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl,
cinnolinyl, 1H-indazolyl, 2H-indazolyl, indolizinyl, isobenzofuyl,
naphthyridinyl, phthalazinyl, pteridinyl, purinyl,
oxazolopyridinyl, thiazolopyridinyl, imidazopyridinyl,
furopyridinyl, thienopyridinyl, pyridopyrimidinyl, pyridopyrazinyl,
pyridopyridazinyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl
groups, and the like. Further examples of heteroaryl groups include
4,5,6,7-tetrahydroindolyl, tetrahydroquinolinyl,
benzothienopyridinyl, benzofuropyridinyl groups, and the like. In
some embodiments, heteroaryl groups can be substituted as described
herein.
[0038] Compounds of the present teachings can include a "divalent
group" defined herein as a linking group capable of forming a
covalent bond with two other moieties. For example, compounds of
the present teachings can include a divalent C.sub.1-20 alkyl group
(e.g., a methylene group), a divalent C.sub.2-20 alkenyl group
(e.g., a vinylyl group), a divalent C.sub.2-20 alkynyl group (e.g.,
an ethynylyl group). a divalent C.sub.6-14 aryl group (e.g., a
phenylyl group); a divalent 3-14 membered cycloheteroalkyl group
(e.g., a pyrrolidylyl), and/or a divalent 5-14 membered heteroaryl
group (e.g., a thienylyl group). Generally, a chemical group (e.g.,
--Ar--) is understood to be divalent by the inclusion of the two
bonds before and after the group.
[0039] The electron-donating or electron-withdrawing properties of
several hundred of the most common substituents, reflecting all
common classes of substituents have been determined, quantified,
and published. The most common quantification of electron-donating
and electron-withdrawing properties is in terms of Hammett .sigma.
values. Hydrogen has a Hammett .sigma. value of zero, while other
substituents have Hammett .sigma. values that increase positively
or negatively in direct relation to their electron-withdrawing or
electron-donating characteristics. Substituents with negative
Hammett .sigma. values are considered electron-donating, while
those with positive Hammett .sigma. values are considered
electron-withdrawing. See Lange's Handbook of Chemistry, 12th ed.,
McGraw Hill, 1979, Table 3-12, pp. 3-134 to 3-138, which lists
Hammett .sigma. values for a large number of commonly encountered
substituents and is incorporated by reference herein.
[0040] It should be understood that the term "electron-accepting
group" can be used synonymously herein with "electron acceptor" and
"electron-withdrawing group". In particular, an
"electron-withdrawing group" ("EWG") or an "electron-accepting
group" or an "electron-acceptor" refers to a functional group that
draws electrons to itself more than a hydrogen atom would if it
occupied the same position in a molecule. Examples of
electron-withdrawing groups include, but are not limited to,
halogen or halo (e.g., F, Cl, Br, I), --NO.sub.2, --CN, --NC,
--S(R.sup.0).sub.2+, --N(R.sup.0).sub.3+, --SO.sub.3H, --SO.sub.2R,
--SO.sub.3R, --SO.sub.2NHR, --SO.sub.2N(R.sup.0).sub.2, --COOH,
--COR.sup.0, --COOR.sup.0, --CONHR.sup.0, --CON(R.sup.0).sub.2,
C.sub.1-40 haloalkyl groups, C.sub.6-14 aryl groups, and 5-14
membered electron-poor heteroaryl groups; where R.sup.0 is a
C.sub.1-20 alkyl group, a C.sub.2-20 alkenyl group, a C.sub.2-20
alkynyl group, a C.sub.1-20 haloalkyl group, a C.sub.1-20 alkoxy
group, a C.sub.6-14 aryl group, a C.sub.3-14 cycloalkyl group, a
3-14 membered cycloheteroalkyl group, and a 5-14 membered
heteroaryl group, each of which can be optionally substituted as
described herein. For example, each of the C.sub.1-20 alkyl group,
the C.sub.2-20 alkenyl group, the C.sub.2-20 alkynyl group, the
C.sub.1-20 haloalkyl group, the C.sub.1-20 alkoxy group, the
C.sub.6-14 aryl group, the C.sub.3-14 cycloalkyl group, the 3-14
membered cycloheteroalkyl group, and the 5-14 membered heteroaryl
group can be optionally substituted with 1-5 small
electron-withdrawing groups such as F, Cl, Br, --NO.sub.2, --CN,
--NC, --S(R.sup.0).sub.2.sup.+, --N(R.sup.0).sub.3.sup.+,
--SO.sub.3H, --SO.sub.2R.sup.0, --SO.sub.3R.sup.0,
--SO.sub.2NHR.sup.0, --SO.sub.2N(R.sup.0).sub.2, --COOH,
--COR.sup.0, --COOR.sup.0, --CONHR.sup.0, and
--CON(R.sup.0).sub.2.
[0041] It should be understood that the term "electron-donating
group" can be used synonymously herein with "electron donor". In
particular, an "electron-donating group" or an "electron-donor"
refers to a functional group that donates electrons to a
neighboring atom more than a hydrogen atom would if it occupied the
same position in a molecule. Examples of electron-donating groups
include --OH, --OR.sup.0, --NH.sub.2, --NHR.sup.0,
--N(R.sup.0).sub.2, and 5-14 membered electron-rich heteroaryl
groups, where R.sup.0 is a C.sub.1-20 alkyl group, a C.sub.2-20
alkenyl group, a C.sub.2-20 alkynyl group, a C.sub.6-14 aryl group,
or a C.sub.3-14 cycloalkyl group.
[0042] Various unsubstituted heteroaryl groups can be described as
electron-rich (or .pi.-excessive) or electron-poor (or
.pi.-deficient). Such classification is based on the average
electron density on each ring atom as compared to that of a carbon
atom in benzene. Examples of electron-rich systems include
5-membered heteroaryl groups having one heteroatom such as furan,
pyrrole, and thiophene; and their benzofused counterparts such as
benzofuran, benzopyrrole, and benzothiophene. Examples of
electron-poor systems include 6-membered heteroaryl groups having
one or more heteroatoms such as pyridine, pyrazine, pyridazine, and
pyrimidine; as well as their benzofused counterparts such as
quinoline, isoquinoline, quinoxaline, cinnoline, phthalazine,
naphthyridine, quinazoline, phenanthridine, acridine, and purine.
Mixed heteroaromatic rings can belong to either class depending on
the type, number, and position of the one or more heteroatom(s) in
the ring. See Katritzky, A. R and Lagowski, J. M., Heterocyclic
Chemistry (John Wiley & Sons, New York, 1960).
[0043] At various places in the present specification, substituents
are disclosed in groups or in ranges. It is specifically intended
that the description include each and every individual
subcombination of the members of such groups and ranges. For
example, the term "C.sub.1-6 alkyl" is specifically intended to
individually disclose C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5,
C.sub.6, C.sub.1-C.sub.6, C.sub.1-C.sub.5, C.sub.1-C.sub.4,
C.sub.1-C.sub.3, C.sub.1-C.sub.2, C.sub.2-C.sub.6, C.sub.2-C.sub.5,
C.sub.2-C.sub.4, C.sub.2-C.sub.3, C.sub.3-C.sub.6, C.sub.3-C.sub.5,
C.sub.3-C.sub.4, C.sub.4- C.sub.6, C.sub.4-C.sub.5, and
C.sub.5-C.sub.6 alkyl. By way of other examples, an integer in the
range of 0 to 40 is specifically intended to individually disclose
0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
36, 37, 38, 39, and 40, and an integer in the range of 1 to 20 is
specifically intended to individually disclose 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Additional
examples include that the phrase "optionally substituted with 1-5
substituents" is specifically intended to individually disclose a
chemical group that can include 0, 1, 2, 3, 4, 5, 0-5, 0-4, 0-3,
0-2, 0-1, 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5
substituents.
[0044] Compounds described herein can contain an asymmetric atom
(also referred as a chiral center) and some of the compounds can
contain two or more asymmetric atoms or centers, which can thus
give rise to optical isomers (enantiomers) and geometric isomers
(diastereomers). The present teachings include such optical and
geometric isomers, including their respective resolved
enantiomerically or diastereomerically pure isomers (e.g., (+) or
(-) stereoisomer) and their racemic mixtures, as well as other
mixtures of the enantiomers and diastereomers. In some embodiments,
optical isomers can be obtained in enantiomerically enriched or
pure form by standard procedures known to those skilled in the art,
which include, for example, chiral separation, diastereomeric salt
formation, kinetic resolution, and asymmetric synthesis. The
present teachings also encompass cis- and trans-isomers of
compounds containing alkenyl moieties (e.g., alkenes, azo, and
imines). It also should be understood that the compounds of the
present teachings encompass all possible regioisomers in pure form
and mixtures thereof. In some embodiments, the preparation of the
present compounds can include separating such isomers using
standard separation procedures known to those skilled in the art,
for example, by using one or more of column chromatography,
thin-layer chromatography, simulated moving-bed chromatography, and
high-performance liquid chromatography. However, mixtures of
regioisomers can be used similarly to the uses of each individual
regioisomer of the present teachings as described herein and/or
known by a skilled artisan.
[0045] It is specifically contemplated that the depiction of one
regioisomer includes any other regioisomers and any regioisomeric
mixtures unless specifically stated otherwise.
[0046] As used herein, a "leaving group" ("LG") refers to a charged
or uncharged atom (or group of atoms) that can be displaced as a
stable species as a result of, for example, a substitution or
elimination reaction. Examples of leaving groups include, but are
not limited to, halogen (e.g., Cl, Br, I), azide (N.sub.3),
thiocyanate (SCN), nitro (NO.sub.2), cyanate (CN), water
(H.sub.2O), ammonia (NH.sub.3), and sulfonate groups (e.g.,
OSO.sub.2--R, wherein R can be a C.sub.1-10 alkyl group or a
C.sub.6-14 aryl group each optionally substituted with 1-4 groups
independently selected from a C.sub.1-10 group and an
electron-withdrawing group) such as tosylate (toluenesulfonate,
OTs), mesylate (methanesulfonate, OMs), brosylate
(p-bromobenzenesulfonate, OBs), nosylate (4-nitrobenzenesulfonate,
ONs), and triflate (trifluoromethanesulfonate, OTf).
[0047] Throughout the specification, structures may or may not be
presented with chemical names. Where any question arises as to
nomenclature, the structure prevails.
[0048] The present teachings relate to polymer-polymer blend
semiconductor materials that include an electron-donor polymer and
an electron-acceptor polymer, where the polymer-polymer blend
semiconductor materials can provide unexpectedly high power
conversion efficiencies (PCEs) when used as the photoactive layer
in optoelectronic devices such as OPV cells. More specifically,
both the electron-acceptor polymer and the electron-donor polymer
can be described as .pi.-conjugated polymers, where repeat units in
the polymer backbone are made up of atoms with sp.sup.2 and .pi.
covalent bonds resulting in alternating double and single bonds
along the polymer backbone. The electron-acceptor polymer and the
electron-donor polymer have different electron affinities and
optical energy gaps.
[0049] Specifically, the electron-donor polymer has a lower
electron affinity (or lower ionization energy) than the
electron-acceptor polymer and therefore functions as a p-type
(hole-transporting) conduction area in the blend. Conversely, the
electron-acceptor polymer has a higher electron affinity (or higher
ionization energy) than the electron-donor polymer and therefore
functions as an n-type (electron-transporting) conduction area in
the blend. In addition, the electron-acceptor polymer can be
characterized by both a lower E.sub.HOMO (highest occupied
molecular orbital energy level) and a lower E.sub.LUMO (lowest
unoccupied molecular orbital energy) that those of the
electron-donor polymer. In preferred embodiments, the E.sub.HOMO of
the electron-acceptor polymer can be at least about -0.3 eV lower
than the E.sub.HOMO of the electron-donor polymer, while the
E.sub.LUMO of the electron-acceptor polymer can be about at least
about -0.3 eV lower than the E.sub.LUMO of the electron-donor
polymer.
[0050] The inventors have discovered that various embodiments of a
polymer-polymer blend ("all-polymer blend") that include an
electron-transporting polymer which is a copolymer comprising an
aromatic fused-ring diimide unit in its backbone, and a
hole-transporting polymer which is a copolymer comprising one or
more thienyl or thienothienyl units and at least one electron-poor
unit in its backbone, unexpectedly can lead to power conversion
efficiencies (PCEs) greater than about 3.0% when incorporated as
the photoactive layer in OPV cells. The electron-transporting
polymer is referred herein interchangeably as the electron-acceptor
polymer, while the hole-transporting polymer is referred herein
interchangeably as the electron-donor polymer. The
electron-transporting polymer typically exhibits an electron
mobility greater than about 10.sup.-5 cm.sup.2/Vs, preferably,
greater than about 10.sup.-3 cm.sup.2/Vs, and more preferably,
greater than about 10.sup.-2 cm.sup.2/Vs; while the
hole-transporting polymer typically exhibits a hole mobility
greater than about 10.sup.-5 cm.sup.2/Vs, preferably, greater than
about 10.sup.-3 cm.sup.2/Vs, and more preferably, greater than
about 10.sup.-2 cm.sup.2/Vs. Particularly, while
poly(3-hexylthiophene) has been investigated as an electron-donor
polymer in certain all-polymer photovoltaic devices, to the
inventors' knowledge, there has been no report to date of any
all-polymer photovoltaic devices with a power conversion efficiency
(PCEs) greater than about 3.0% which includes an electron-donor
polymer comprising one or more electron-poor units. As described in
more detailed below, the electron-poor unit can be selected from an
electron-poor 8-20 membered polycyclic heteroaryl group and a
chlorinated 5-20 membered heteroaryl group. Without wishing to be
bound by any particular theory, it is believed that the
unexpectedly high power conversion efficiencies can be a result of
advantageous donor/acceptor pairing in terms of a low bandgap
between the HOMO of the donor polymer and the LUMO of the acceptor
polymer, fine-tuned LUMO-LUMO energy offset, combined optical
absorption across the solar spectrum, and/or improved charge
transport characteristics due to optimized blend
morphology/microstructure relating to favorable intermolecular
interaction between the donor polymer and the acceptor polymer.
[0051] The aromatic fused-ring diimide-based acceptor polymer in
the present polymer-polymer blend can be an alternating or random
copolymer where the other repeat unit(s) (i.e., the repeat unit(s)
that do not include any aromatic fused-ring diimides) can include
one or more conjugated moieties such as one or more monocyclic or
polycyclic C.sub.6-20 aryl moieties or 5-20 membered heteroaryl
moieties. A aromatic fused-ring diimide may be referred herein
interchangeably as a bis(imide)arene unit. In certain embodiments,
the aromatic fused-ring diimide-based acceptor polymer can be an
alternating polymer represented by Formula 1:
##STR00002##
wherein: .pi.-1 is an optionally substituted fused ring moiety;
R.sup.1 is selected from the group consisting of a C.sub.1-30 alkyl
group, a C.sub.2-30 alkenyl group, a C.sub.1-30 haloalkyl group, a
C.sub.6-20 aryl group and a 5-14 membered heteroaryl group, wherein
the C.sub.6-20 aryl group and the 5-14 membered heteroaryl group
optionally are substituted with a C.sub.1-30 alkyl group, a
C.sub.2-30 alkenyl group, or a C.sub.1-30 haloalkyl group; M.sup.a
is a repeat unit comprising one or more conjugated moieties that
does not include a rylene diimide; and n is an integer in the range
of 2 to 5,000.
[0052] In certain embodiments, the aromatic fused-ring
diimide-based acceptor polymer can be a random polymer represented
by Formula 2:
##STR00003##
wherein: .pi.-1 and .pi.-1' can be identical or different and
independently are an optionally substituted fused ring moiety;
R.sup.1 and R.sup.1' can be identical or different and
independently are selected from the group consisting of a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, a C.sub.1-30
haloalkyl group, a C.sub.6-20 aryl group and a 5-14 membered
heteroaryl group, wherein the C.sub.6-20 aryl group and the 5-14
membered heteroaryl group optionally are substituted with a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, or a C.sub.1-30
haloalkyl group; M.sup.a and M.sup.a' can be identical or different
and independently are a repeat unit comprising one or more
conjugated moieties that does not include a rylene diimide; p and q
independently are a real number, wherein 0.1.ltoreq.p.ltoreq.0.9,
0.1.ltoreq.q.ltoreq.0.9, and the sum of p and q is about 1; and n
is an integer in the range of 2 to 5,000; provided that at least
one of the following is true: (a) .pi.-1' is different from .pi.-1,
(b) R.sup.1 is different from R.sup.1, or (c) M.sup.a' is different
from M.sup.a.
[0053] In various embodiments, the aromatic fused-ring diimide can
be selected from the group consisting of a perylene diimide, a
naphthalene diimide, an anthracene diimide, a coronene diimide, and
a dithienocoronene diimide, with .pi.-1 and .pi.-1' independently
being a fused ring moiety selected from the group consisting
of:
##STR00004##
[0054] The one or more conjugated moieties in the co-repeat unit
M.sup.a and M.sup.a' can be represented by Ar, .pi.-2, and Z,
wherein Ar is an optionally substituted monocyclic aryl or
heteroaryl group, .pi.-2 is an optionally substituted polycyclic
conjugated moiety, and Z is a conjugated linear linker. In various
embodiments, M.sup.a and M.sup.a' can have a formula selected
from:
##STR00005##
wherein m, m' and m'' independently are 0, 1, 2, 3, 4, 5 or 6.
[0055] For example, in some embodiments, .pi.-2 can be a polycyclic
C.sub.8-24 aryl group or a polycyclic 8-24 membered heteroaryl
group, wherein each of these groups can be optionally substituted
with 1-6 R.sup.e groups, wherein: [0056] R.sup.e, at each
occurrence, is independently a) halogen, b) --CN, c) --NO.sub.2, d)
oxo, e) --OH, f) .dbd.C(R').sub.2, g) a C.sub.1-40 alkyl group, h)
a C.sub.2-40 alkenyl group, i) a C.sub.2-40 alkynyl group, j) a
C.sub.1-40 alkoxy group, k) a C.sub.1-40 alkylthio group, 1) a
C.sub.1-40 haloalkyl group, m) a --Y--C.sub.3-10 cycloalkyl group,
n) a --Y--C.sub.6-14 aryl group, [0057] o) a --Y--C.sub.6-14
haloaryl group, p) a --Y-3-12 membered cycloheteroalkyl group, or
q) a --Y-5-14 membered heteroaryl group, wherein each of the
C.sub.1-40 alkyl group, the C.sub.2-40 alkenyl group, the
C.sub.2-40 alkynyl group, the C.sub.3-10 cycloalkyl group, the
C.sub.6-14 aryl group, the C.sub.6-14 haloaryl group, the 3-12
membered cycloheteroalkyl group, and the 5-14 membered heteroaryl
group is optionally substituted with 1-4 R.sup.f groups; [0058]
R.sup.f, at each occurrence, is independently a) halogen, b) --CN,
c) --NO.sub.2, d) oxo, e) --OH, f) --NH.sub.2, g) --NH(C.sub.1-20
alkyl), h) --N(C.sub.1-20 alkyl).sub.2, i) --N(C.sub.1-20
alkyl)-C.sub.6-14 aryl, j) --N(C.sub.6-14 aryl).sub.2, k)
--S(O).sub.wH, l) --S(O).sub.w--C.sub.1-20 alkyl, m)
--S(O).sub.2OH, n) --S(O).sub.w--OC.sub.1-20 alkyl, o)
--S(O).sub.w--OC.sub.6-14 aryl, p) --CHO, q) --C(O)--C.sub.1-20
alkyl, r) --C(O)--C.sub.6-14 aryl, s) --C(O)OH, t)
--C(O)--OC.sub.1-20 alkyl, u) --C(O)--OC.sub.6-14 aryl, v)
--C(O)NH.sub.2, w) --C(O)NH--C.sub.1-20 alkyl, x)
--C(O)N(C.sub.1-20 alkyl).sub.2, y) --C(O)NH--C.sub.6-14 aryl, z)
--C(O)N(C.sub.1-20 alkyl)-C.sub.6-14 aryl, aa) --C(O)N(C.sub.6-14
aryl).sub.2, ab) --C(S)NH.sub.2, ac) --C(S)NH--C.sub.1-20 alkyl,
ad) --C(S)N(C.sub.1-20 alkyl).sub.2, ae) --C(S)N(C.sub.6-14
aryl).sub.2, af) --C(S)N(C.sub.1-20 alkyl)-C.sub.6-14 aryl, ag)
--C(S)NH--C.sub.6-14 aryl, ah) --S(O).sub.wNH.sub.2, ai)
--S(O).sub.wNH(C.sub.1-20 alkyl), aj) --S(O).sub.wN(C.sub.1-20
alkyl).sub.2, ak) --S(O).sub.wNH(C.sub.6-14 aryl), al)
--S(O).sub.wN(C.sub.1-20 alkyl)-C.sub.6-14 aryl, am)
--S(O).sub.wN(C.sub.6-14 aryl).sub.2, an) --SiH.sub.3, ao)
--SiH(C.sub.1-20 alkyl).sub.2, ap) --SiH.sub.2(C.sub.1-20 alkyl),
aq) --Si(C.sub.1-20 alkyl).sub.3, ar) a C.sub.1-20 alkyl group, as)
a C.sub.2-20 alkenyl group, at) a C.sub.2-20 alkynyl group, au) a
C.sub.1-20 alkoxy group, av) a C.sub.1-20 alkylthio group, aw) a
C.sub.1-20 haloalkyl group, ax) a C.sub.3-10 cycloalkyl group, ay)
a C.sub.6-14 aryl group, az) a C.sub.6-14 haloaryl group, ba) a
3-12 membered cycloheteroalkyl group, or bb) a 5-14 membered
heteroaryl group; [0059] Y, at each occurrence, is independently
selected from a divalent C.sub.1-6 alkyl group, a divalent
C.sub.1-6 haloalkyl group, and a covalent bond; and [0060] w is 0,
1, or 2.
[0061] To illustrate, in certain embodiments, .pi.-2 can be
selected from:
##STR00006## ##STR00007##
wherein: k, k', l and l' independently can be selected from
--CR.sup.2.dbd., .dbd.CR.sup.2--, --C(O)--, and --C(C(CN).sub.2)--;
p, p', q and q' independently can be selected from --CR.sup.2.dbd.,
.dbd.CR.sup.2--, --C(O)--, --C(C(CN).sub.2)--, --O--, --S--,
--N.dbd., .dbd.N--, --N(R.sup.2)--, --SiR.sup.2.dbd.,
.dbd.SiR.sup.2--, and --SiR.sup.2R.sup.2--; r and s independently
can be --CR.sup.2R.sup.2-- or --C(C(CN).sub.2)--; u, u', v and v'
independently can be selected from --CR.sup.2.dbd.,
.dbd.CR.sup.2--, --C(O)--, --C(C(CN).sub.2)--, --S--, --S(O)--,
--S(O).sub.2--, --O--, --N.dbd., .dbd.N--, --SiR.sup.2.dbd.,
.dbd.SiR.sup.2--, --SiR.sup.2R.sup.2--,
--CR.sup.2R.sup.2--CR.sup.2R.sup.2--, and
--CR.sup.2.dbd.CR.sup.2--; and R.sup.2, at each occurrence,
independently can be H or R.sup.e, wherein R.sup.e is as defined
herein.
[0062] In certain embodiments, .pi.-2 can be selected from:
##STR00008## ##STR00009## ##STR00010## ##STR00011##
where k, l, p, p', q, q', r, s and R.sup.2 are as defined herein.
In some embodiments, k and l independently can be selected from
--CR.sup.2.dbd., .dbd.CR.sup.2--, and --C(O)--; p, p', q, and q'
independently can be selected from --O--, --S--, --N(R.sup.2)--,
--N.dbd., .dbd.N--, --CR.sup.2.dbd., and .dbd.CR.sup.2--; u and v
independently can be selected from --CR.sup.2.dbd.,
.dbd.CR.sup.2--, --C(O)--, --C(C(CN).sub.2)--, --S--, --O--,
--N.dbd., .dbd.N--, --CR.sup.2R.sup.2--CR.sup.2R.sup.2--, and
--CR.sup.2.dbd.CR.sup.2--; where R.sup.2 is as defined herein. For
example, R.sup.2, at each occurrence, independently can be selected
from H, a halogen, --CN, --OR.sup.c, --N(R.sup.c).sub.2, a
C.sub.1-20 alkyl group, and a C.sub.1-20 haloalkyl group, where
R.sup.c is as defined herein. Each of r and s can be CH.sub.2.
[0063] In certain embodiments, .pi.-2 can be a polycyclic moiety
including one or more thienyl, thiazolyl, or phenyl groups, where
each of these groups can be optionally substituted as disclosed
herein. For example, .pi.-2 can be selected from:
##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016##
##STR00017##
wherein R.sup.2 is as defined herein. For example, R.sup.2 can be
selected from H, a C.sub.1-20 alkyl group, a C.sub.1-20 alkoxy
group, and a C.sub.1-20 haloalkyl group.
[0064] In some embodiments, Ar, at each occurrence, independently
can be an optionally substituted monocyclic moiety selected
from:
##STR00018##
wherein: a, b, c and d independently are selected from --S--,
--O--, --CH.dbd., .dbd.CH--, --CR.sup.3.dbd., .dbd.CR.sup.3--,
--C(O)--, --C(C(CN).sub.2)--, --N.dbd., .dbd.N--, --NH-- and
--NR.sup.3--; R.sup.3, at each occurrence, is independently
selected from a) halogen, b) --CN, c) --NO.sub.2, d)
--N(R.sup.c).sub.2, e) --OR.sup.c, f) --C(O)R.sup.c, g)
--C(O)OR.sup.c, h) --C(O)N(R).sub.2, i) a C.sub.1-40 alkyl group,
j) a C.sub.2-40 alkenyl group, k) a C.sub.2-40 alkynyl group, l) a
C.sub.1-40 alkoxy group, m) a C.sub.1-40 alkylthio group, n) a
C.sub.1-40 haloalkyl group, o) a --Y--C.sub.3-14 cycloalkyl group,
p) a --Y--C.sub.6-14 aryl group, q) a --Y-3-14 membered
cycloheteroalkyl group, and r) a --Y-5-14 membered heteroaryl
group, wherein each of the C.sub.1-40 alkyl group, the C.sub.2-40
alkenyl group, the C.sub.2-40 alkynyl group, the C.sub.3-14
cycloalkyl group, the C.sub.6-14 aryl group, the 3-14 membered
cycloheteroalkyl group, and the 5-14 membered heteroaryl group
optionally is substituted with 1-5 R.sup.e groups; R.sup.c, at each
occurrence, is independently selected from H, a C.sub.1-6alkyl
group, and a --Y--C.sub.6-14 aryl group; Y and R.sup.e are as
defined herein.
[0065] In certain embodiments, each Ar can be independently a 5- or
6-membered aryl or heteroaryl group. For example, each Ar can be
selected from a phenyl group, a thienyl group, a furyl group, a
pyrrolyl group, an isothiazolyl group, a thiazolyl group, a
1,2,4-thiadiazolyl group, a 1,3,4-thiadiazolyl group, and a
1,2,5-thiadiazolyl group, wherein each group can be divalent or
monovalent, and optionally can be substituted with 1-4 substituents
independently selected from a halogen, --CN, an oxo group, a
C.sub.1-6alkyl group, a C.sub.1-6alkoxy group, a C.sub.1-6
haloalkyl group, NH.sub.2, NH(C.sub.1-6alkyl) and
N(C.sub.1-6alkyl).sub.2. In particular embodiments, each Ar can be
selected from a thienyl group, an isothiazolyl group, a thiazolyl
group, a 1,2,4-thiadiazolyl group, a 1,3,4-thiadiazolyl group, a
1,2,5-thiadiazolyl group, a phenyl group, and a pyrrolyl group,
wherein each group optionally can be substituted with 1-2
substituents independently selected from a halogen, --CN, an oxo
group, a C.sub.1-6alkyl group, a C.sub.1-6alkoxy group, a
C.sub.1-6haloalkyl group, NH.sub.2, NH(C.sub.1-6alkyl) and
N(C.sub.1-6alkyl).sub.2. In some embodiments, Ar can be
unsubstituted. In some embodiments, Ar can be a thienyl group, an
isothiazolyl group, a thiazolyl group, a 1,2,4-thiadiazolyl group,
a 1,3,4-thiadiazolyl group, and a 1,2,5-thiadiazolyl group, wherein
each optionally is substituted with 1-2 C.sub.1-6alkyl groups.
[0066] By way of example, (Ar).sub.m, (Ar).sub.m', and (Ar).sub.m''
can be selected from:
##STR00019##
wherein R.sup.4, at each occurrence, independently is H or R.sup.3,
and R.sup.3 is as defined herein. In particular embodiments,
##STR00020##
can be selected from:
##STR00021##
wherein R.sup.c is as defined herein.
[0067] In various embodiments, the linker Z can be a conjugated
system by itself (e.g., including two or more double or triple
bonds) or can form a conjugated system with its neighboring
components. For example, in embodiments where Z is a linear linker,
Z can be a divalent ethenyl group (i.e., having one double bond), a
divalent ethynyl group (i.e., having one tripe bond), a C.sub.4-40
alkenyl or alkynyl group that includes two or more conjugated
double or triple bonds, or some other non-cyclic conjugated systems
that can include heteroatoms such as Si, N, P, and the like. For
example, Z can be selected from:
##STR00022##
wherein R.sup.4 is as defined herein. In certain embodiments, Z can
be selected from:
##STR00023##
[0068] In some embodiments, M.sup.a and M.sup.a' can include at
least one optionally substituted monocylic aryl or heteroaryl
group. For example, M.sup.a and M.sup.a' can have the formula:
##STR00024##
wherein m'' is selected from 1, 2, 3, 4, 5, or 6; and Ar is as
defined herein. For example, M.sup.a and M.sup.a' can be selected
from:
##STR00025## ##STR00026##
wherein R.sup.3 and R.sup.4 are as defined herein. In particular
embodiments, M.sup.a and M.sup.a' can be selected from:
##STR00027##
wherein R.sup.3 can be independently selected from a halogen, --CN,
a C.sub.1-20 alkyl group, a C.sub.1-20 alkoxy group, and a
C.sub.1-20 haloalkyl group; R.sup.4 can be independently selected
from H, a halogen, --CN, a C.sub.1-20 alkyl group, a C.sub.1-20
alkoxy group, and a C.sub.1-20 haloalkyl group; and R.sup.c, at
each occurrence, can be independently H or a C.sub.1-6alkyl
group.
[0069] In some embodiments, M.sup.a and M.sup.a', in addition to
the one or more optionally substituted monocyclic aryl or
heteroaryl group, can include a linker. For example, M.sup.a and
M.sup.a' can have the formula:
##STR00028##
wherein m and m' are selected from 1, 2, 4, or 6; m'' is selected
from 1, 2, 3, or 4; and Ar and Z are as defined herein. In certain
embodiments, M.sup.a and M.sup.a' can be selected from:
##STR00029##
wherein R.sup.4 and R.sup.c are as defined herein.
[0070] In some embodiments, M.sup.a and M.sup.a', in addition to
the one or more optionally substituted monocyclic aryl or
heteroaryl group, can include one or more optionally substituted
polycyclic moieties. For example, M.sup.a and M.sup.a' can have the
formula:
##STR00030##
wherein m and m' are selected from 1, 2, 4, or 6; and Ar and .pi.-2
are as defined herein. In certain embodiments, M.sup.a and M.sup.a'
can be selected from:
##STR00031##
wherein R.sup.2 and R.sup.4 are as defined herein.
[0071] In some embodiments, M.sup.a and M.sup.a', in addition to
the one or more optionally substituted monocyclic aryl or
heteroaryl group, can include one or more linkers and/or optionally
substituted polycyclic moieties. For example, M.sup.a and M.sup.a'
can have a formula selected from:
##STR00032##
wherein m, m' and m'' independently are 1, 2, 3 or 4; and Ar,
.pi.-2 and Z are as defined herein.
[0072] In certain embodiments, M.sup.a and M.sup.a' can be selected
from
##STR00033##
wherein R.sup.4 is as defined herein.
[0073] In other embodiments, M.sup.a and M.sup.a' can have a
formula selected from: selected from
##STR00034##
wherein .pi.-2 and Z are as defined herein.
[0074] To illustrate, M.sup.a and M.sup.a' can be selected from the
group consisting of:
##STR00035##
wherein g, h, i and j independently can be selected from
--CR.sup.2.dbd., .dbd.CR.sup.2--, --S--, --N.dbd., .dbd.N--, and
--N(R.sup.2)--; R.sup.2 and R, at each occurrence, independently
can be H or R.sup.e; and R.sup.e is as defined herein.
[0075] In particular embodiments, the electron-acceptor polymer of
the present polymer-polymer blend can be represented by Formula 3
or 4:
##STR00036##
wherein: .pi.-1 and .pi.-1' can be identical or different and
independently are an optionally substituted fused ring moiety;
R.sup.1 and R.sup.1' can be identical or different and
independently are selected from the group consisting of a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, a C.sub.1-30
haloalkyl group, a C.sub.6-20 aryl group and a 5-14 membered
heteroaryl group, wherein the C.sub.6-20 aryl group and the 5-14
membered heteroaryl group optionally are substituted with a
C.sub.1-30 alkyl group, a C.sub.2-30 alkenyl group, or a C.sub.1-30
haloalkyl group; R' and R'' can be identical or different and
independently are selected from the group consisting of H, F, Cl,
--CN, and -L-R, wherein L, at each occurrence, independently is
selected from the group consisting of --O--, --S--, --C(O),
--C(O)O--, and a covalent bond; and R, at each occurrence,
independently can be selected from the group consisting of a
C.sub.6-20 alkyl group, a C.sub.6-20 alkenyl group, and a
C.sub.6-20 haloalkyl group; m and m' independently can be 1, 2, 3,
4, 5 or 6; and p and q independently are a real number, wherein
0.1.ltoreq.p.ltoreq.0.9, 0.1.ltoreq.q.ltoreq.0.9, and the sum of p
and q is about 1; and n is an integer in the range of 2 to 5,000;
provided that at least one of the following is true: (a) .pi.-1' is
different from .pi.-1, (b) R.sup.1' is different from R.sup.1, or
(c) R'' is different from R'.
[0076] To illustrate further, embodiments of the electron-acceptor
polymer of the present polymer-polymer blend can be represented by
Formula 5, 6, 7, or 8:
##STR00037##
wherein R.sup.1, R.sup.1', p, q, and n are as defined herein.
[0077] For example, R.sup.1 and R.sup.1' can be selected from the
group consisting of a branched C.sub.3-20 alkyl group, a branched
C.sub.4-20 alkenyl group, and a branched C.sub.3-20 haloalkyl group
such as:
##STR00038##
[0078] The donor polymer in the present polymer-polymer blend can
have an alternating push-pull structure represented by formula
9:
##STR00039##
where the donor subunit (D) includes a bridged dithiophene moiety
selected from the group consisting of a benzodithiophene moiety, a
naphthodithiophene moiety, a thienodithiophene moiety, and a
pyridodithiophene moiety; the acceptor subunit (A) includes an
electron-poor conjugated moiety; and either the donor subunit (D)
or the acceptor subunit (A) comprises one or more thienyl or
thienothienyl groups. For example, the bridged dithiophene moiety
of the donor subunit (D) can be selected from the group consisting
of:
##STR00040##
where R.sup.a, at each occurrence, independently can be selected
from the group consisting of -L'-R.sup.b, -L'-Ar', and
-L'-Ar'--Ar', where L' is selected from the group consisting of
--O--, --S--, --C(O)O--, --OC(O)--, and a covalent bond; R.sup.b is
selected from the group consisting of a C.sub.3-40 alkyl group, a
C.sub.3-40 alkenyl group, and a C.sub.3-40 haloalkyl group; and
Ar', at each occurrence, independently is a 5-14 membered
heteroaryl group optionally substituted with 1-2 R.sup.b
groups.
[0079] For example, in certain embodiments, R.sup.a can be selected
from the group consisting of a linear C.sub.5-40 alkyl group, a
branched C.sub.5-40 alkyl group, a linear C.sub.5-40 alkoxy group,
a branched C.sub.5-40 alkoxy group, a linear C.sub.5-40 alkylthio
group, and a branched C.sub.5-40 alkylthio group. Accordingly,
using benzodithiophene as the representative donor subunit, D can
be selected from the group consisting of:
##STR00041##
where R.sup.b, at each occurrence, can be a linear or branched
C.sub.5-40 alkyl group.
[0080] In other embodiments, each R.sup.a can be -L'-Ar' or
-L'-Ar'--Ar', where L' and Ar' are as defined herein. For example,
each Ar' can be a thienyl group or a thienyl-fused polycyclic
group, each of which can be optionally substituted as described
herein. To illustrate, the bridged dithiophene moiety can be
functionalized with a thienyl group, a bithienyl group, or a
thienyl-fused polycyclic group, each of which can be optionally
substituted as described herein. To illustrate further, and using
benzodithiophene again as the representative donor subunit, D can
be selected from the group consisting of:
##STR00042## ##STR00043##
can be selected from the group consisting of:
##STR00044##
each of which can be optionally substituted with 1-2 R.sup.b
groups, and R.sup.b, at each occurrence, independently can be a
C.sub.3-40 alkyl group.
[0081] In further embodiments, the donor subunit (D) can have a
formula selected from
##STR00045##
wherein: Ar.sup.1 and Ar.sup.2 independently are an optionally
substituted C.sub.6-14 aryl group or an optionally substituted 5-14
membered heteroaryl group; Ar.sup.3 and Ar.sup.4 independently are
an optionally substituted phenyl group or an optionally substituted
5- or 6-membered heteroaryl group; L, at each occurrence,
independently is selected from --O--, --S--, --Se--, --OC(O)--,
--C(O)O--, a divalent C.sub.1-20 alkyl group, a divalent C.sub.1-20
haloalkyl group, and a covalent bond; L.sup.1, at each occurrence,
independently is selected from --O--, --S--, --Se--, --OC(O)--,
--C(O)O--, a divalent C.sub.1-20 alkyl group, and a divalent
C.sub.1-20 haloalkyl group; U and U' independently are selected
from --O--, --S--, and --Se--; V and V' independently are --CR.dbd.
or --N.dbd.; W, at each occurrence, independently is selected from
--O--, --S--, and --Se--; W', at each occurrence, independently is
--CR.dbd. or --N.dbd.; and R, at each occurrence, independently is
selected from H, a halogen, --CN, and L'R', wherein L', at each
occurrence, is selected from --O--, --S--, --Se--, --C(O)--,
--OC(O)--, --C(O)O--, and a covalent bond; and R', at each
occurrence, independently is selected from a C.sub.1-40 alkyl
group, a C.sub.2-40 alkenyl group, a C.sub.2-40 alkynyl group, and
a C.sub.1-40 haloalkyl group.
[0082] In certain embodiments, each of U, U' and W can be --S--,
and each of V, V' and W' can be --CH.dbd. or --CCl.dbd., thus
providing a it group having a formula selected from:
##STR00046## ##STR00047##
wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, L and L.sup.1 are
as defined herein. To illustrate, L and L.sup.1 can be selected
from --O--, --S--, --OC(O)--, --C(O)O--, a divalent C.sub.1-20
alkyl group, and a covalent bond.
[0083] In certain embodiments, the donor subunit (D) can include a
chlorinated bridged-dithiophene unit. Examples of chlorinated
bridged-dithiophene unit include:
##STR00048## ##STR00049##
wherein R.sup.b, at each occurrence, independently can be a
C.sub.3-40 alkyl group.
[0084] In some embodiments, the donor subunit (D) can include one
or more thienyl groups optionally substituted with 1-2 alkoxy
groups.
[0085] The acceptor subunit (A) includes an electron-poor
conjugated moiety (6). In certain embodiments, the electron-poor
conjugated moiety can be an 8-14 membered polycyclic heteroaryl
moiety including either at least one ring that has two or more
heteroatoms selected from N and S, and/or at least one ring that is
substituted with one or more electron-withdrawing groups such as F,
Cl, an oxo group, a carbonyl group, a carboxylic ester group, or a
sulfonyl group. In particular embodiments, the electron-poor
conjugated moiety can be flanked by optionally substituted thienyl
or thieno[3,2-b]thiophenyl groups. In certain embodiments, the
electron-poor conjugated moiety (6) can include one or more
chlorinated thienyl groups.
[0086] Accordingly, in various embodiments, the acceptor subunit
(A) can be represented by the formula:
##STR00050##
where .delta. represents the electron-poor conjugated moiety, and
R.sup.c, at each occurrence, can be H or R, where R, at each
occurrence, independently can be selected from the group consisting
of a C.sub.6-20 alkyl group, a C.sub.6-20 alkenyl group, and a
C.sub.6-20 haloalkyl group.
[0087] Examples of electron-poor conjugated moieties (.delta.)
include, but are not limited to:
##STR00051## ##STR00052##
where R.sup.d, at each occurrence, independently can be selected
from a C.sub.3-40 alkyl group, a C.sub.3-40 alkenyl group, and a
C.sub.3-40 haloalkyl group; and R.sup.f, at each occurrence,
independently can be selected from the group consisting of H, F,
Cl, --CN, --S(O).sub.2--C.sub.1-20 alkyl, --C(O)--OC.sub.1-20
alkyl, --C(O)--C.sub.1-20 alkyl, a C.sub.1-20 alkyl group, a
C.sub.2-20 alkenyl group, a C.sub.1-20 alkoxy group, a C.sub.1-20
alkylthio group, and a C.sub.1-20 haloalkyl group. For example,
R.sup.d, at each occurrence, independently can be a linear or
branched C.sub.6-20 alkyl group; and R.sup.f, at each occurrence,
independently can be selected from H, F, Cl, C(O)R.sup.e,
C(O)OR.sup.e, and S(O).sub.2R.sup.e; where R.sup.e, at each
occurrence, independently can be a linear or branched C.sub.6-20
alkyl group.
[0088] Accordingly, in some embodiments, the electron donor polymer
can be an alternating copolymer having the formula 10, 11, or
12:
##STR00053##
wherein: R.sup.a, at each occurrence, can be selected from the
group consisting of -L'-R.sup.b, -L'-Ar', and -L'-Ar'--Ar', where
L' is selected from the group consisting of --O--, --S--, and a
covalent bond; R.sup.b is selected from the group consisting of a
C.sub.3-40 alkyl group, a C.sub.3-40 alkenyl group, and a
C.sub.3-40 haloalkyl group; and Ar', at each occurrence,
independently is a 5-14 membered heteroaryl group optionally
substituted with 1-2 R.sup.b groups; R.sup.c, at each occurrence,
is H or R, where R, at each occurrence, independently is selected
from the group consisting of a C.sub.6-20 alkyl group, a C.sub.6-20
alkenyl group, and a C.sub.6-20 haloalkyl group; .delta. is
selected from the group consisting of:
##STR00054## ##STR00055##
where R.sup.d, at each occurrence, independently can be selected
from a C.sub.3-40 alkyl group, a C.sub.3-40 alkenyl group, and a
C.sub.3-40 haloalkyl group; and R.sup.f, at each occurrence,
independently can be selected from the group consisting of H, F,
Cl, --CN, --S(O).sub.2--C.sub.1-20 alkyl, --C(O)--OC.sub.1-20
alkyl, --C(O)--C.sub.1-20 alkyl, a C.sub.1-20 alkyl group, a
C.sub.2-20 alkenyl group, a C.sub.1-20 alkoxy group, a C.sub.1-20
alkylthio group, and a C.sub.1-20 haloalkyl group. For example,
R.sup.d, at each occurrence, independently can be a linear or
branched C.sub.6-20 alkyl group; and R.sup.f, at each occurrence,
independently can be selected from H, F, Cl, C(O)R.sup.e,
C(O)OR.sup.e, and S(O).sub.2R.sup.e; where R.sup.e, at each
occurrence, independently can be a linear or branched C.sub.6-20
alkyl group; and n is an integer in the range of 2 to 5,000.
[0089] In other embodiments, the electron donor polymer can be a
random copolymer having the formula 13 or 14:
##STR00056##
wherein: R.sup.a, at each occurrence, can be selected from the
group consisting of -L'-R.sup.b, -L'-Ar', and -L'-Ar'--Ar', where
L' is selected from the group consisting of --O--, --S--, and a
covalent bond; R.sup.b is selected from the group consisting of a
C.sub.3-40 alkyl group, a C.sub.3-40 alkenyl group, and a
C.sub.3-40 haloalkyl group; and Ar', at each occurrence,
independently is a 5-14 membered heteroaryl group optionally
substituted with 1-2 R.sup.b groups; R, at each occurrence,
independently can be a C.sub.6-20 alkyl group; .delta., at each
occurrence, independently can be selected from the group consisting
of:
##STR00057## ##STR00058##
where R.sup.d, at each occurrence, independently can be selected
from a C.sub.3-40 alkyl group, a C.sub.3-40 alkenyl group, and a
C.sub.3-40 haloalkyl group; and R.sup.f, at each occurrence,
independently can be selected from the group consisting of H, F,
Cl, --CN, --S(O).sub.2--C.sub.1-20 alkyl, --C(O)--OC.sub.1-20
alkyl, --C(O)--C.sub.1-20 alkyl, a C.sub.1-20 alkyl group, a
C.sub.2-20 alkenyl group, a C.sub.1-20 alkoxy group, a C.sub.1-20
alkylthio group, and a C.sub.1-20 haloalkyl group. For example,
R.sup.d, at each occurrence, independently can be a linear or
branched C.sub.6-20 alkyl group; and R.sup.f, at each occurrence,
independently can be selected from H, F, Cl, C(O)R.sup.e,
C(O)OR.sup.e, and S(O).sub.2R.sup.e; where R.sup.e, at each
occurrence, independently can be a linear or branched C.sub.6-20
alkyl group; x and y independently are a real number, wherein
0.1.ltoreq.x.ltoreq.0.9, 0.1.ltoreq.y.ltoreq.0.9, and the sum of x
and y is about 1; and n is an integer in the range of 2 to
5,000.
[0090] Accordingly, the present polymer-polymer blend can include
an electron acceptor polymer according to any of formula 1-8 and an
electron donor polymer according to any of formula 10-14. In
certain preferred embodiments, the present polymer-polymer blend
can include an electron acceptor polymer according to formula 5-8
and an electron donor polymer that is an alternating copolymer of a
formula selected from the group consisting of:
##STR00059## ##STR00060##
where R.sup.b, at each occurrence, can be a linear or branched
C.sub.3-40 alkyl group; R.sup.c, at each occurrence, can be H or a
C.sub.6-20 alkyl group; and n can be an integer in the range of 5
to 5,000.
[0091] In other preferred embodiments, the present polymer-polymer
blend can include an electron acceptor polymer according to any of
formula 5-8 and an electron donor polymer that is a random
copolymer of a formula selected from the group consisting of:
##STR00061## ##STR00062## ##STR00063## ##STR00064##
where R.sup.b, at each occurrence, can be a linear or branched
C.sub.3-40 alkyl group; R, at each occurrence, can be a C.sub.6-20
alkyl group; x and y independently are a real number, wherein
0.1.ltoreq.x.ltoreq.0.9, 0.1.ltoreq.y.ltoreq.0.9
(0.2.ltoreq.x.ltoreq.0.8, 0.2.ltoreq.y.ltoreq.0.8), and the sum of
x and y is about 1; and n can be an integer in the range of 5 to
5,000.
[0092] In certain preferred embodiments, the present
polymer-polymer blend can include an electron acceptor polymer
according to any of formula 5-8 and an electron donor polymer that
is an alternating copolymer of a formula selected from the group
consisting of:
##STR00065## ##STR00066## ##STR00067## ##STR00068##
where R.sup.b, R.sup.d, R.sup.e, at each occurrence, independently
can be a linear or branched C3-40 alkyl group; R.sup.e, at each
occurrence, can be H or a C6-20 alkyl group; R.sup.f, at each
occurrence, independently can be selected from H, F, Cl,
C(O)R.sup.e, C(O)OR.sup.e, and S(O).sub.2R.sup.e; where R.sup.e, at
each occurrence, independently can be a linear or branched
C.sub.6-20 alkyl group; r can be 0 or 1; and n can be an integer in
the range of 5 to 5,000. In certain embodiments, the electron donor
polymer can be a random copolymer having two repeat units of any of
formula 43-56. For example, the electron donor polymer can be a
random copolymer having two repeat units of formula 43, where in
one repeat unit, r is 1 and R.sup.c is H, and in the other repeat
unit r is 1 and R.sup.c is a C.sub.6-20 alkyl group.
[0093] Illustrative examples of embodiments where the electron
donor polymer includes a naphthodithiophene moiety as the donor
subunit can include:
##STR00069##
where R.sup.b, R.sup.d, R.sup.f, R, x, y, and n are as defined
herein.
[0094] Illustrative examples of embodiments where the electron
donor polymer includes one or more chlorinated groups can
include:
##STR00070## ##STR00071## ##STR00072## ##STR00073##
where R.sup.a can be -L'-Ar' or -L'-Ar'--Ar', where L' is selected
from the group consisting of --O--, --S--, --C(O)O--, --OC(O)--,
and a covalent bond; each Ar' can be a thienyl group or a
thienyl-fused polycyclic group, each of which can be optionally
substituted as described herein; R.sup.b, at each occurrence, can
be a linear or branched C.sub.3-40 alkyl group; R, at each
occurrence, can be a C.sub.6-20 alkyl group; x and y independently
are a real number, wherein 0.1.ltoreq.x.ltoreq.0.9,
0.1.ltoreq.y.ltoreq.0.9 (0.2.ltoreq.x.ltoreq.0.8,
0.2.ltoreq.y.ltoreq.0.8), and the sum of x and y is about 1; and n
can be an integer in the range of 5 to 5,000.
[0095] Electron-donor polymers and electron-acceptor polymers
according to the present teachings and monomers leading to them can
be prepared according to procedures analogous to those described in
the Examples. In particular, Stille coupling or Suzuki coupling
reactions can be used to prepare co-polymeric compounds according
to the present teachings with high molecular weights and in high
yields (.gtoreq.75%) and purity, as confirmed by .sup.1H NMR
spectra, elemental analysis, and/or GPC measurements.
Alternatively, the present polymers can be prepared from
commercially available starting materials, compounds known in the
literature, or via other readily prepared intermediates, by
employing standard synthetic methods and procedures known to those
skilled in the art. Standard synthetic methods and procedures for
the preparation of organic molecules and functional group
transformations and manipulations can be readily obtained from the
relevant scientific literature or from standard textbooks in the
field.
[0096] The electron-donor polymers and electron-acceptor polymers
in the present polymer-polymer blends can be soluble in various
common organic solvents. As used herein, a polymer can be
considered soluble in a solvent when at least 0.1 mg of the polymer
can be dissolved in 1 mL of the solvent. Examples of common organic
solvents include petroleum ethers; acetonitrile; aromatic
hydrocarbons such as benzene, toluene, xylene, and mesitylene;
ketones such as acetone, and methyl ethyl ketone; ethers such as
tetrahydrofuran, dioxane, bis(2-methoxyethyl) ether, diethyl ether,
di-isopropyl ether, and t-butyl methyl ether; alcohols such as
methanol, ethanol, butanol, and isopropyl alcohol; aliphatic
hydrocarbons such as hexanes; esters such as methyl acetate, ethyl
acetate, methyl formate, ethyl formate, isopropyl acetate, and
butyl acetate; amides such as dimethylformamide and
dimethylacetamide; sulfoxides such as dimethylsulfoxide;
halogenated aliphatic and aromatic hydrocarbons such as
dichloromethane, chloroform, ethylene chloride, chlorobenzene,
dichlorobenzene, and trichlorobenzene; and cyclic solvents such as
cyclopentanone, cyclohexanone, and 2-methypyrrolidone. In preferred
embodiments, the solvent can be selected from the group consisting
of chlorobenzene, dichlorobenzene (o-dichlorobenzene,
m-dichlorobenzene, p-dichlorobenzene, or mixtures thereof),
trichlorobenzene, benzene, toluene, chloroform, dichloromethane,
dichloroethane, xylenes, .alpha.,.alpha.,.alpha.-trichlorotoluene,
methyl naphthalene (e.g., 1-methylnaphthalene, 2-methylnaphthalene,
or mixtures thereof), chloronaphthalene (e.g., 1-chloronaphthalene,
2-chloronaphthalene, or mixtures thereof), and mixtures
thereof.
[0097] The electron-donor polymers and electron-acceptor polymers
described herein can be dissolved, dispersed or suspended in a
single solvent or mixture of solvents to provide a blend
composition suitable for solution processing techniques. Common
solution processing techniques include, for example, spin coating,
slot coating, doctor blading, drop-casting, zone casting, dip
coating, blade coating, or spraying. Another example of solution
processing technique is printing. As used herein, "printing"
includes a noncontact process such as inkjet printing,
microdispensing and the like, and a contact process such as
screen-printing, gravure printing, offset printing, flexographic
printing, lithographic printing, pad printing, microcontact
printing and the like.
[0098] An organic photoactive semiconductor component can be
prepared as a blended film deposited from a solution or dispersion
containing a polymer-polymer blend according to the present
teachings. For example, an all-polymer blend according to the
present teachings can be dissolved in chloroform, chlorobenzene, or
a mixture thereof, where the electron-donor and electron-acceptor
polymers together can be present in the solution from about 0.5 wt
% to about 10 wt %, preferably, from about 0.8 wt % to about 5 wt
%, and more preferably, from about 1 wt % to about 3 wt %. The
weight ratio of the electron-donor polymers to the
electron-acceptor polymers in the blend can be from about 20:1 to
about 1:20, for example, from about 10:1 to about 1:10, preferably
from about 5:1 to about 1:5, from about 3:1 to about 1:3, from
about 2: to about 1:2, and more preferably about 1:1. The
photoactive layer also can contain a polymeric binder, which can be
present from about 5 to about 95% by weight. The polymeric binder,
for example, can be a semicrystalline polymer selected from
polystyrene (PS), high density polyethylene (HDPE), polypropylene
(PP) and polymethylmethacrylate (PMMA). In some embodiments, the
polymeric blend can be used together with additional components
that are optically active, for example, components that can assist
in light harvesting by capturing and transferring excitons to one
or both of the electron-donor polymers/electron-acceptor polymers
in the blend, and/or optically non-active components to modify
and/or improve processing and/or device performance. Such optically
non-active components can include alkanethiols (e.g.,
alkanedithiols) and other .alpha.,.omega.-functionalized alkanes
(e.g., diiodoalkanes) as known in the art. See e.g., U.S. Pat. No.
8,227,691.
[0099] An organic semiconductor film can be prepared from a
polymeric blend according to the present teachings in any form that
provides for separation of electron-hole pairs. In some
embodiments, the organic semiconductor film can be in a planar
bilayer form. In other embodiments, the organic semiconductor film
can be in a bilayer form with a diffuse interface. In preferred
embodiments, the organic semiconductor film can be a single layer
in a bulk heterojunction (BHJ) form. As used herein, a "film" means
a continuous piece of a substance having a high length to thickness
ratio and a high width to thickness ratio.
[0100] An organic semiconductor film prepared from an all-polymer
blend according to the present teachings can be photoactive because
the electron-donor polymers and/or the electron-acceptor polymers
therein are capable of absorbing photons to generate excitons for
the generation of a photocurrent. Accordingly, the present
all-polymer blend can be used to prepare a photoactive component in
an optoelectronic device, where the photoactive component or layer
can be fabricated by first preparing a blend composition (e.g., a
solution or dispersion) that includes an electron-donor polymer and
an electron-acceptor polymer disclosed herein dissolved or
dispersed in a liquid medium such as a solvent or a mixture of
solvents, depositing the blend composition on a substrate (e.g., an
electrode-substrate) preferably via a solution-phase process, and
removing the solvent or mixture of solvents to provide the
photoactive layer. By having the blend composition provided as an
intimate mixture of the electron-donor polymers and the
electron-acceptor polymers, bulk heterojunctions can be created
upon removal of the solvent (optionally under reduced pressure
and/or elevated temperature), during which nanoscale phase
separation of the electron-donor polymers and the electron-acceptor
polymers takes place. In some embodiments, the depositing step can
be carried out by printing, including inkjet printing and various
contact printing techniques (e.g., screen-printing, gravure
printing, offset printing, pad printing, lithographic printing,
flexographic printing, and microcontact printing). In other
embodiments, the depositing step can be carried out by spin
coating, slot-die coating, drop-casting, zone casting, dip coating,
blade coating, or spraying. When the film is formed by spin
coating, the spin speed can range from about 300 rpm to about 6000
rpm, or from about 500 rpm to about 2000 rpm. Subsequent processing
steps can include thermal annealing or irradiation of the deposited
film. For example, the blended film can be annealed from about
50.degree. C. to about 300.degree. C., preferably from about
70.degree. C. to about 200.degree. C., more preferably from about
90.degree. C. to about 180.degree. C. for about 1 min to about 20
minutes. The annealing step can be carried out under an inert
atmosphere (e.g., under nitrogen). Irradiation of the deposited
film can be carried out using infrared light or ultraviolet light.
As used herein, "annealing" refers to a post-deposition heat
treatment to the semicrystalline polymer film in ambient or under
reduced/increased pressure for a time duration of more than 60
seconds, and "annealing temperature" refers to the maximum
temperature that the polymer film is exposed to for at least 30
seconds during this process of annealing. Without wishing to be
bound by any particular theory, it is believed that annealing can
result in improved PCEs of the all-polymer blend. Furthermore, an
advantage of the present all-polymer blend can include improved
stability during the annealing step compared to known
polymer:fullerene blends. The photoactive layer typically can have
a thickness ranging from about 30 nm to about 500 nm. In preferred
embodiments, the photoactive layer can be a thin film having a
thickness of about 80-300 nm.
[0101] Optoelectronic devices that can incorporate a photoactive
layer prepared from an all-polymer blend according to the present
teachings include, but are not limited to, photovoltaic/solar
cells, photodetectors (or photodiodes), light-emitting diodes, and
light-emitting transistors. The present polymeric blends can offer
processing and operation advantages in the fabrication and/or the
use of these devices.
[0102] For example, articles of manufacture such as the various
devices described herein can be an optoelectronic device including
a first electrode, a second electrode, and a photoactive component
disposed between the first electrode and the second electrode,
where the photoactive component includes a polymeric blend of the
present teachings.
[0103] In various embodiments, the optoelectronic device can be
configured as a solar cell, in particular, a bulk-heterojunction
solar cell. FIG. 1 illustrates a representative structure of a
bulk-heterojunction organic solar cell which can incorporate a
polymeric blend according to the present teachings. As shown, a
representative solar cell generally includes a substrate 20, an
anode 22, a cathode 26, and a photoactive layer 24 between the
anode and the cathode. In some embodiments, one or more optional
interlayers can be present between the anode and the photoactive
layer and/or between the cathode and the photoactive layer.
[0104] The substrate can be a solid, rigid or flexible layer
designed to provide robustness to the device. In preferred
embodiments, the substrate can be transparent or semi-transparent
in the spectral region of interest. As used herein, a material is
considered "transparent" when it has transmittance over 50%, and a
material is considered "semi-transparent" when it has transmittance
between about 50% and about 5%. The substrate can comprise any
suitable material known in the art such as glass or a flexible
plastic (polymer) film.
[0105] The first and second electrodes should have different work
functions, with the electrode having the higher work function at or
above about 4.5 eV (the "high work function electrode") serving as
the hole-injecting electrode or anode, and the electrode having the
lower work function at or below about 4.3 eV (the "low work
function electrode") serving as the electron-injecting electrode.
In a traditional OPV device structure, the high work function
electrode or anode typically is composed of a transparent
conducting metal oxide or metal sulfide such as indium tin oxide
(ITO), gallium indium tin oxide (GITO), and zinc indium tin oxide
(ZITO), or a thin, transparent layer of gold or silver. The low
work function electrode or cathode typically is composed of a low
work function metal such as aluminum, indium, calcium, barium, and
magnesium. The electrodes can be deposited by thermal vapor
deposition, electron beam evaporation, RF or Magnetron sputtering,
chemical vapor deposition or the like.
[0106] In various embodiments, the solar cell can include one or
more optional interface layers ("interlayers") between the anode
and the photoactive layer and/or between the cathode and the
photoactive layer. For example, in some embodiments, an optional
smoothing layer (e.g., a film of 3,4-polyethylenedioxythiophene
(PEDOT), or 3,4-polyethylenedioxythiophene:polystyrene-sulfonate
(PEDOT:PSS)) can be present between the anode and the photoactive
layer. The optional interlayer(s) can perform other functions such
as reducing the energy barrier between the photoactive layer and
the electrode, forming selective contacts for a single type of
carrier (e.g., a hole-blocking layer), modifying the work function
of the adjacent electrode, and/or protecting the underlying
photoactive layer. In some embodiments, a transition metal oxide
layer such as V.sub.2O.sub.5, MoO.sub.3, WO.sub.3 and NiO can be
deposited on top of the ITO anode, instead of using PEDOT or
PEDOT:PSS as the p-type buffer. To improve device stability via
modification of the cathode, an n-type buffer composed of LiF, CsF
or similar fluorides can be provided between the cathode and the
photoactive layer. Other n-type buffer materials include TiO.sub.x,
ZnO.sub.x and Cs-doped TiO.sub.x. Depending on the composition, the
interlayers can be solution-processed (e.g., sol-gel deposition,
self-assembled monolayers) or deposited by vacuum processes such as
thermal evaporation or sputtering.
[0107] In certain embodiments, a solar cell according to the
present teachings can include a transparent glass substrate onto
which an electrode layer (anode) made of indium tin oxide (ITO) is
applied. This electrode layer can have a relatively rough surface,
and a smoothing layer made of a polymer, typically PEDOT:PSS made
electrically conductive through doping, can be applied on top of
the electrode layer to enhance its surface morphology. Other
similar interlayers can be optionally present between the anode and
the photoactive layer for improving mechanical, chemical, and/or
electronic properties of the device. The photoactive layer is
composed of an all-polymer blend as described above, and can have a
layer thickness of, e.g., about 80 nm to a few .mu.m. Before a
counter electrode (cathode) is applied, an electrically insulating
transition layer can be applied onto the photoactive layer. This
transition layer can be made of an alkali halide, e.g., LiF, and
can be vapor-deposited in vacuum. Again, similar to the anode,
other similar interlayers can be optionally present between the
photoactive layer and the cathode for improving mechanical,
chemical, and/or electronic properties of the device.
[0108] In certain embodiments, a solar cell according to the
present teachings can have an inverted device structure, where a
modified ITO film is used as the cathode. For example, the ITO can
be modified by n-type metal oxides or metal carbonates such as
TiO.sub.x, ZnO.sub.x, Cs-doped TiO.sub.x, and caesium carbonate. In
particular embodiments, the inverted OPV can include a
solution-processed ZnO.sub.x n-type interface layer as described in
Lloyd et al., "Influence of the hole-transport layer on the initial
behavior and lifetime of inverted organic photovoltaics," Solar
Energy Materials and Solar Cells, 95(5): 1382-1388 (2011). Compared
with the traditional device structure, inverted-type devices can
demonstrate better long-term ambient stability by avoiding the need
for the corrosive and hygroscopic hole-transporting PEDOT:PSS and
low work function metal cathode. The anode of an inverted OPV cell
can be composed of Ag, Au, and the like, with an optional p-type
interface layer composed of transition metal oxides such as
V.sub.2O.sub.5, MoO.sub.3, WO.sub.3 and NiO.
EXAMPLES
[0109] The following examples are provided to illustrate further
and to facilitate the understanding of the present teachings and
are not in any way intended to limit the invention.
[0110] All reagents were purchased from commercial sources and used
without further purification unless otherwise noted.
Characterization data are provided in some cases by .sup.1H-NMR,
.sup.13C-NMR, and/or elemental analysis. NMR spectra were recorded
on an Inova 500 NMR spectrometer (.sup.1H, 500 MHz). Elemental
analyses were performed by Midwest Microlab, LLC.
[0111] Preparation of Electron-Acceptor Polymers
Example 1
Preparation of poly{[N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2EH-T2)]
[0112] Preparation of
2,6-dibromonaphthalene-1,4,5,8-tetracarboxydianhydride
(NDA-Br.sub.2): A mixture of 1,4,5,8-naphthalenetetracarboxylic
dianhydride (2.8 g, 10.3 mmol) and oleum (20% SO.sub.3, 100 mL) was
stirred at 55.degree. C. for 2 hours. To this mixture, a solution
of dibromoisocyanuric acid (3.0 g, 10.5 mmol) in oleum (50 mL) was
added over 40 minutes. The resulting mixture was then warmed to
85.degree. C. and maintained at this temperature for 43 hours.
After cooling to room temperature, the reaction mixture was poured
onto crushed ice (420 g), diluted with water (400 mL), and then
stirred at room temperature for 1 hour. The resulting precipitates
were collected by centrifugation, washed with water and methanol,
collected by centrifugation and finally dried under vacuum, leading
to a greenish yellow solid (3.6 g, 8.5 mmol, yield 82.2%).
Elemental Analysis (calc. C, 39.47; H, 0.47; N, 0.00). found C,
38.20; H, 0.79; N, 0.00.
[0113] Preparation of
N,N'-bis(2-ethylhexyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide)
(NDI2EH-Br.sub.2): A mixture of NDA-Br.sub.2 (above, 1.6 g, 3.9
mmol), 2-ethylhexylamine (1.4 mL, 8.5 mmol), o-xylene (6 mL), and
propionic acid (2 mL) was stirred at 140.degree. C. for 1 hour.
After cooling to room temperature, methanol (10 mL) was added to
the reaction mixture and the resulting precipitate was collected by
filtration, washed with methanol, and dried in vacuum leading to
the crude product as a red solid (0.81 g). Further purification was
carried out by column chromatography on silica gel using a mixture
of chloroform:hexane (5:1, v/v) as eluent, affording a slightly
yellow solid as the product (0.61 g, 0.94 mmol, yield 24.4%).
.sup.1H NMR (CDCl.sub.3, 500 MHz): .delta. 9.01 (s, 2H), 4.10-4.25
(m, 4H), 19.4-1.97 (m, 2H), 1.20-1.40 (m, 16H), 0.87-1.03 (m, 12H).
.sup.13C NMR (CDCl.sub.3, 125 MHz): .delta. 161.4, 161.2, 139.4,
128.6, 127.9, 125.5, 124.3, 45.3, 38.0, 30.8, 28.7, 24.2, 23.3,
14.3, 10.8.
[0114] Preparation of P(NDI2EH-T2): Under argon, a mixture of
NDI2EH-Br.sub.2 (above, 98 mg, 0.15 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (74 mg, 0.15 mmol), and
Pd(PPh.sub.3).sub.2Cl.sub.2 (3.5 mg, 0.005 mmol) in anhydrous
toluene (5 mL) was stirred at 90.degree. C. for 4 days.
Bromobenzene (0.3 mL) was then added to the reaction and the
resulting mixture was stirred for an additional 12 hours. After
cooling to room temperature, a solution of potassium fluoride (1.2
g) in water (2.5 mL) was added. This mixture was stirred at room
temperature for 2 hours and the precipitate was collected by
filtration. The solid was taken with a small amount of chloroform,
methanol was added, and the solid collected by filtration. This
procedure was repeated using chloroform and acetone, leading to a
deep blue solid as the crude product. This crude product was
purified by Soxhlet extraction with acetone for 24 hours (80 mg,
yield 80.7%). .sup.1H NMR (CDCl.sub.3, 500 MHz): .delta. 8.82 (br,
2H), 7.35 (br, 4H), 4.15 (br, 4H), 1.97 (br, 2H), 1.18-1.70 (m, br,
16H). 0.80-1.12 (m, br, 12H). Elemental Analysis (calc. C, 69.91;
H, 6.18; N, 4.29). found C, 69.63; H, 5.66; N, 3.71.
Example 2
Preparation of poly{[N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-2,5-thiophene} [P(NDI2EH-T1)]
[0115] Preparation of P(NDI2EH-T1): Under argon, a mixture of
NDI2EH-Br.sub.2 (Example 1, 84 mg, 0.13 mmol),
2,5-bis(trimethylstannyl)thiophene (53 mg, 0.13 mmol), and
Pd(PPh.sub.3).sub.2Cl.sub.2 (3.0 mg, 0.004 mmol) in anhydrous
toluene (5 mL) was stirred at 90.degree. C. for 4 days.
Bromobenzene (0.3 mL) was then added and the resulting mixture was
stirred at 90.degree. C. for an additional 12 hours. Upon cooling
to room temperature, a solution of potassium fluoride (1.2 g) in
water (2.5 mL) was added. This mixture was stirred at room
temperature for 2 hours and the precipitate collected by
filtration. The solid was taken with a small amount of chloroform,
methanol was added, and the resulting solid collected by
filtration. This procedure was repeated using chloroform and
acetone, leading to a deep blue solid as the crude product (20.0
mg, yield 20.7%). Elemental Analysis (calc. C, 71.55; H, 6.71; N,
4.91). found C, 71.59; H, 6.00; N, 4.56.
Example 3
Preparation of Poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)]
[0116] Preparation of 1-iodo-2-octyldodecane: Iodine (12.25 g, 48.3
mmol) was added to a solution of 2-octyl-1-dodecanol (12.42 g, 41.6
mmol), triphenylphosphine (13.17 g, 50.2 mmol), and imidazole (3.42
g, 50.2 mmol) in 80 mL dichloromethane at 0.degree. C. After
stirring for 30 minutes, the reaction mixture was allowed to warm
to room temperature over 4 hours before 12 mL of saturated
Na.sub.2SO.sub.3 (aq) was added. The organics were concentrated by
evaporation and the mixture taken up in 500 mL pentane, washed
three times with 200 mL water, and once with 150 mL brine. The
mixture was then passed through a 3 cm silica gel plug, and dried
over Na.sub.2SO.sub.4. The organics were concentrated by
evaporation to give a colorless oil (15.78 g, yield 92.9%). .sup.1H
NMR (CDCl.sub.3 500 MHz): .delta.: 2.60 (d, J=5.0 Hz, 2H), 2.00 (t,
J=5.0 Hz, 1H), 1.30-1.20 (b, 32H), 0.89 (t, J=7.5 Hz, 6H); MS (EI):
m/z (%) 408.23 (100) [M+]. Elemental Analysis (calc. C, 58.81; H,
10.12). found C, 58.70; H, 9.97.
[0117] Preparation of 2-octyldodecylamine: 1-Iodo-2-octyldodecane
(5.90 g, 14.5 mmol) and potassium phthalimide (2.94 g, 15.9 mmol)
were dissolved in 25 mL of DMF and vigorously stirred for 72 h at
25.degree. C. The reaction mixture was poured into 200 mL of
pentane, and washed four times with 100 mL water. The mixture was
then passed through a 3 cm silica gel plug, and concentrated to
give a colorless oil. The oil was next dissolved in 150 mL of
ethanol, and 4 mL of hydrazine hydrate were added, leading to a
mixture which was heated to reflux overnight. The resulting
precipitates were collected by filtration, dissolved in 100 mL
water, and the solution was made alkaline by addition of 6 M NaOH
(aq). The resulting mixture was dissolved in 200 mL pentane, washed
four times with 100 mL of water, once with 70 mL of brine, dried
over MgSO.sub.4, and concentrated to give a colorless oil (3.08 g,
72% yield). .sup.1H NMR (CDCl.sub.3 500 MHz): .delta.: 2.60 (d,
J=5.0 Hz, 2H), 2.00 (t, J=5.0 Hz, 1H), 1.30-1.20 (b, 32H), 0.89 (t,
J=7.5 Hz, 6H); MS (EI): m/z (%) 297.34 (100) [M+]. Elemental
Analysis (calc. C, 80.73; H, 14.57). found C, 80.78; H, 14.52.
[0118] Preparation of
N,N'-bis(2-octyldodecyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide-
) (NDI2OD-Br.sub.2): A mixture of NDA-Br.sub.2 (Example 1, 2.34 g,
5.49 mmol), 2-octyldodecylamine (4.10 g, 13.78 mmol), o-xylene (18
mL), and propionic acid (6 mL) was stirred at 140.degree. C. for 1
hour. Upon cooling to room temperature, most of the solvent was
removed in vacuo, and the residue was purified by a column
chromatography on silica gel with a mixture of chloroform:hexane
(1:1, v/v) as the eluent, affording a slightly yellow solid as the
product (1.98 g, 2.01 mmol, yield 36.7%). .sup.1H NMR (CDCl.sub.3
500 MHz): .delta.: 8.95 (s, 2H), 4.12 (d, J=7.5 Hz, 4H), 1.97 (m,
2H), 1.20-1.40 (m, 64H), 0.84-0.89 (m, 12H). .sup.13C NMR
(CDCl.sub.3, 125 MHz): .delta.: 161.3, 161.1, 139.3, 128.5, 127.8,
125.4, 124.2, 45.6, 36.6, 32.1, 32.0, 31.7, 30.2, 29.9, 29.8, 29.7,
29.6, 29.5, 26.5, 22.9, 22.8, 14.3. Elemental Analysis (calc. C,
65.84; H, 8.60; N, 2.84). found C, 65.68; H, 8.60; N, 2.89.
[0119] Preparation of P(NDI2OD-T2): Under argon, a mixture of
NDI-2OD-Br.sub.2 (95 mg, 0.096 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (48 mg, 0.096 mmol),
and Pd(PPh.sub.3).sub.2Cl.sub.2 (3.5 mg, 0.005 mmol) in anhydrous
toluene (5 mL) was stirred at 90.degree. C. for 4 days.
Bromobenzene (0.2 mL) was then added and the reaction mixture was
maintained at 90.degree. C. for an additional 12 hours. Upon
cooling to room temperature, a solution of potassium fluoride (1 g)
in water (2 mL) was added. This mixture was stirred at room
temperature for 2 hours before it was extracted with chloroform (60
mL.times.2). Organic layers were combined, washed with water (50
mL.times.2), dried over anhydrous sodium sulfate, and concentrated
on a rotary evaporator. The residue was taken with a small amount
of chloroform and precipitated in methanol and acetone in sequence.
The obtained blue solid product was purified by Soxhlet extraction
with acetone for 48 hours. The remaining solid residue was
redissolved in chloroform (50 mL) and the resulting mixture was
heated to boil. Upon cooling to room temperature, the chloroform
solution was filtered through a 5 .mu.m filter, and the filtrate
was added slowly to methanol (50 mL). The precipitates were
collected by filtration, washed with methanol, and dried in vacuum,
leading to a deep blue solid as the product (88.0 mg, yield 92.1%).
.sup.1H NMR (CDCl.sub.3 500 MHz): .delta.: 8.53-8.84 (m, br, 2H),
7.20-7.48 (br, 4H), 4.13 (s, br, 2H), 2.00 (s, br, 4H), 1.05-1.30
(s, br, 64H), 0.87 (s, br, 12H). GPC: M.sub.n=47.8K Da,
M.sub.w=264.4K Da, PDI=5.53. Elemental Analysis (calc. C, 75.26; H,
8.96; N, 2.83; Br, 0.00). found C, 75.22; H, 9.01; N, 2.77; Br,
0.00.
Example 4
Preparation of Poly{[N,N'-bis(1-methylhexyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI1MH-T2)]
[0120] Preparation of
N,N'-bis(1-methylhexyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide)
(NDI1MH-Br.sub.2): A mixture of NDA-Br.sub.2 (Example 1, 2.42 g,
5.68 mmol), 1-methylhexylamine (2.5 mL, 16.55 mmol), propionic acid
(12 mL), and o-xylene (36 mL) was stirred under argon at
140.degree. C. for 17 hours. Upon cooling to room temperature,
solvents were removed in vacuo and the residue was subject to a
column chromatography on silica gel using a mixture of
CHCl.sub.3:hexane (1:1, v/v) as the eluent, leading to slightly
yellow solid as the product (0.24 g, 0.39 mmol, yield 6.9%).
.sup.1H NMR (CDCl.sub.3, 500 MHz): .delta. 8.96 (s, 2H), 5.24 (m,
2H), 2.13 (m, 2H), 1.94 (m, 2H), 1.56 (d, J=7.0 Hz, 6H), 1.10-1.40
(m, 12H), 0.81-0.86 (t, J=7.0 Hz, 6H). .sup.13C NMR (CDCl.sub.3,
125 MHz): .delta.: 161.3, 161.3, 139.3, 128.3, 127.8, 125.7, 124.5,
51.5, 33.5, 31.8, 26.9, 22.7, 18.3, 14.2.
[0121] Preparation of P(NDI1MH-T2): Under argon, a mixture of
NDI1MH-Br.sub.2 (above, 151 mg, 0.24 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (120 mg, 0.24 mmol),
and Pd(PPh.sub.3).sub.2Cl.sub.2 (6.5 mg, 0.009 mmol) in anhydrous
toluene (12 mL) was stirred at 90.degree. C. for 24 hours.
Bromobenzene (0.2 mL) was then added and the reaction mixture was
maintained at 90.degree. C. for an additional 12 hours. Upon
cooling to room temperature, the reaction mixture was added slowly
to methanol (50 mL) and the resulting mixture was stirred at room
temperature for 10 minutes. The precipitates were collected by
filtration and washed with methanol. The isolated solid was then
taken with chloroform (30 mL) and sonicated for 5 minutes. A
solution of potassium fluoride (4 g) in water (8 mL) was added, and
this mixture was vigorously stirred at room temperature for 1 hour.
The mixture was then diluted with chloroform (100 mL), and washed
with water (100 mL.times.2). The organic layer was concentrated on
rotary evaporator. The residue was taken with chloroform (30 mL),
followed by sonication for 5 minutes. This mixture was precipitated
in methanol (150 mL), leading to deep blue precipitates, which were
collected by filtration, washed with methanol, and dried in a
vacuum (143 mg, yield 94%). Further purification involved Soxhlet
extraction with acetone and then another precipitation in methanol.
.sup.1H NMR (CDCl.sub.3, 500 MHz): .delta. 8.70-8.82 (br, 2H),
7.05-7.73 (m, br, 3H), 6.64 (br, 1H), 5.15-5.50 (m, br, 2H),
0.71-2.43 (m, br, 28H).
Example 5
Preparation of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5'''-(quarterthiophene)} [P(NDI2OD-T4)]
[0122] Preparation of
N,N'-bis(2-octyldodecyl)-2,6-bis(2-thienyl)naphthalene-1,4,5,8-bis(dicarb-
oximide) (NDI2OD-T1): Under argon, a mixture of NDI2OD-Br.sub.2
(Example 1, 280.0 mg, 0.28 mmol), 2-trimethylstannylthiophene
(400.0 mg, 1.62 mmol), Pd(PPh.sub.3).sub.2Cl.sub.2 (28.0 mg, 0.04
mmol) in anhydrous toluene (20 mL) was stirred at 90.degree. C. for
22 hours. Upon cooling to room temperature, the reaction mixture
was diluted with chloroform (100 mL), and the resulting mixture was
washed with water (80 mL.times.2), dried over anhydrous sodium
sulfate (Na.sub.2SO.sub.4), and concentrated on rotary evaporator.
The residue was subject to column chromatography on silica gel with
a mixture of chloroform:hexane (3:2, v/v) as eluent, leading to an
orange solid as the product (240.0 mg, 0.24 mmol, 85.2%). .sup.1H
NMR (CDCl.sub.3 500 MHz): .delta.: 8.77 (s, 2H), 7.57 (d, J=5.0 Hz,
2H), 7.31 (d, J=3.5 Hz, 2H), 7.21 (m, 2H), 4.07 (d, J=7.5 Hz, 4H),
1.95 (m, 2H), 1.18-40 (m, br, 64H), 0.84-0.88 (m, 12H); .sup.13C
NMR (CDCl.sub.3 125 MHz): .delta.: 162.8, 162.6, 141.1, 140.4,
136.8, 128.4, 128.2, 127.7, 127.6, 125.6, 123.6, 45.0, 36.6, 32.1,
31.7. 30.3, 29.9, 29.8, 29.7, 29.6, 29.5, 26.6, 22.9, 14.4,
14.3.
[0123] Preparation of
N,N'-bis(2-octyldodecyl)-2,6-bis(5-bromo-2-thienyl)naphthalene-1,4,5,8-bi-
s(dicarboximide) (NDI2OD-BrT1): Under argon, a mixture of NDI2OD-T1
(200.0 mg, 0.20 mmol) and NBS (125.0 mg, 0.70 mmol) in DMF (20 mL)
was stirred at 80.degree. C. for 25 hours. Upon cooling to room
temperature, the reaction mixture was poured into water (100 mL),
and the resulting mixture was extracted with chloroform (100 mL).
The organic layer was separated, washed with water (100
mL.times.2), dried over anhydrous Na.sub.2SO.sub.4, and
concentrated on rotary evaporator. The residue was subject to
column chromatography on silica gel with a mixture of
chloroform:hexane (2:3, v/v, slowly up to 1:1) as eluent, leading
to a red solid as the product (145.0 mg, 0.13 mmol, 62.5%). .sup.1H
NMR (CDCl.sub.3, 500 MHz): .delta.: 8.73 (s, 2H), 7.15 (d, J=4.0
Hz, 2H), 7.09 (d, J=4.0, 2H), 4.08 (d, J=7.5 Hz, 4H), 1.93-1.98 (m,
2H), 1.20-1.40 (br, m, 64H), 0.83-0.89 (m, 12H). Elemental Analysis
(calc. C, 64.79; H, 7.72; N, 2.44). found C, 64.50; H, 7.74; N,
2.49.
[0124] Preparation of P(NDI2OD-T4): Under argon, a mixture of
NDI2OD-BrT1 (92.1 mg, 0.08 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (39.4 mg, 0.08 mmol),
and Pd(PPh.sub.3).sub.2Cl.sub.2 (2.8 mg, 0.004 mmol) in anhydrous
toluene (5 mL) was stirred at 90.degree. C. for 4 days.
Bromobenzene (0.3 mL) was then added and the resulting mixture was
stirred for an additional 12 hours. After cooling to room
temperature, a solution of potassium fluoride (1 g) in water (2 mL)
was added. This mixture was stirred and shaken at room temperature
for 1 hour, before it was diluted with chloroform (150 mL). The
resulting mixture was washed with water (100 mL.times.3), dried
over anhydrous Na.sub.2SO.sub.4, and concentrated on rotary
evaporator. The residue was taken with chloroform (30 mL) and
precipitated in methanol (50 mL). This procedure was repeated using
chloroform and acetone, leading to a dark blue solid as crude
product. This crude product was purified by Soxhlet extraction with
acetone for 48 hours. The isolated solid was dissolved in
chloroform (50 mL) and then heated to boil. After cooling to room
temperature, the chloroform solution was passed through a syringe
filter (5 .mu.m), and the filtrate was precipitated in methanol (50
mL). The precipitates were collected by filtration, washed with
methanol, and dried in vacuum, leading to a dark blue solid (87.0
mg, 94.1%). .sup.1H NMR (CDCl.sub.2CDCl.sub.2, 500 MHz): .delta.:
8.70-8.81 (m, br, 2H), 7.10-7.40 (m, br, 8H), 4.10 (br, 4H), 1.99
(s, br, 2H), 1.10-1.45 (m, br, 64H), 0.86 (m, br, 12H). GPC:
M.sub.n=67.4K Da, M.sub.w=170.3K Da, PDI=2.5. Elemental Analysis
(calc. C, 72.87; H, 8.04; N, 2.43). found C, 72.69; H, 8.06; N,
2.47.
Example 6
Preparation of Poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5'-(2,2'-bithiazole)} [P(NDI2OD-TZ2)]
[0125] Preparation of P(NDI2OD-TZ2): Under argon, a mixture of
NDI2OD-Br.sub.2 (Example 1, 235 mg, 0.239 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiazole (118 mg, 0.239 mmol),
and Pd(PPh.sub.3).sub.2Cl.sub.2 (7.0 mg, 0.010 mmol) in anhydrous
toluene (12 mL) was stirred at 90.degree. C. for 3 days.
Bromobenzene (0.3 mL) was then added and the resulting mixture was
stirred for an additional 12 hours. After cooling to room
temperature, a solution of potassium fluoride (2 g) in water (4 mL)
was added. This mixture was stirred and shaken at room temperature
for 1 hour, before it was diluted with chloroform (150 mL). The
resulting mixture was washed with water (100 mL.times.3), dried
over anhydrous Na.sub.2SO.sub.4, and concentrated on a rotary
evaporator. The residue was taken with chloroform (50 mL) and
precipitated in methanol (100 mL). This procedure was repeated
using chloroform and acetone, leading to a dark red solid as the
crude product. This crude product was purified by Soxhlet
extraction with acetone for 72 hours. The isolated solid was
dissolved in chloroform (80 mL) and then heated to boil. Upon
cooling to room temperature, this chloroform solution was passed
through a syringe filter (5 m), and the filtrate was precipitated
in methanol (80 mL). The precipitates were collected by filtration,
washed with methanol, and dried in vacuum, leading to a dark red
solid (222 mg, 93.7%). .sup.1H NMR (CDCl.sub.3, 500 MHz): .delta.:
7.71 (m, br, 2H), 7.54 (m, br, 2H), 4.20-4.25 (m, br, 4H), 1.69 (m,
br, 2H), 1.15-1.50 (m, br, 64H) 0.80-0.95 (m, br, 12H). Elemental
Analysis (calc. C, 72.68; H, 8.74; N, 5.65). found C, 72.07; H,
8.61; N, 5.56.
Example 7
Preparation of Poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)}
[P(NDI2OD-TBT)]
[0126] Preparation of P(NDI2OD-TBT) (Suzuki Coupling Reaction):
Under argon, a mixture of
N,N'-bis(2-octyldodecyl)-2,6-bis(5'-bromo-2'-thienyl)naphthalene-1,4,5,8--
bis(dicarboximide) (NDI2OD-BrT1) (Example 5, 85.0 mg, 0.074 mmol),
4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazo-
le (28.7 mg, 0.074 mmol), potassium carbonate (81.0 mg, 0.586
mmol), and Pd(PPh.sub.3).sub.4 (1.8 mg, 0.002 mmol) in anhydrous
toluene (4 mL) and DMF (2 mL) was stirred at 100.degree. C. for 3
days. Bromobenzene (0.3 mL) was then added and the resulting
mixture was stirred for an additional 12 hours. After cooling to
room temperature, the reaction mixture was poured into methanol
(200 mL), and the resulting mixture was stirred at room temperature
for 15 minutes. The precipitates were collected by filtration,
washed with methanol, and dried in vacuum, leading a dark solid as
the product (62.0 mg, 74.6%). Elemental Analysis (calc. C, 72.68;
H, 8.07; N, 4.99). found C, 72.41; H, 7.90; N, 5.00.
[0127] Preparation of P(NDI2OD-TBT) (Stille Coupling Reaction):
Under argon, a mixture of NDI2OD-Br.sub.2 (Example 1, 84.3 mg,
0.086 mmol),
5,5-bis(trimethylstannyl)-4',7'-di-2-thienyl)-2',1',3'-benzothiadiazole
(53.6 mg, 0.086 mmol), and Pd(PPh.sub.3).sub.2Cl.sub.2 (2.5 mg,
0.004 mmol) in anhydrous toluene (6.5 mL) was stirred at 90.degree.
C. for 3 days. Bromobenzene (0.3 mL) was then added and the
resulting mixture was stirred for an additional 12 hours. After
cooling to room temperature, a solution of potassium fluoride (1 g)
in water (2 mL) was added. This mixture was stirred and shaken at
room temperature for 1 hour, before it was diluted with chloroform
(150 mL). The resulting mixture was washed with water (100
mL.times.3), dried over anhydrous Na.sub.2SO.sub.4, and
concentrated on a rotary evaporator. The residue was taken with
chloroform (50 mL) and precipitated in methanol (100 mL). This
procedure was repeated using chloroform and acetone, leading to a
dark solid as the crude product (58.0 mg, 60.3%).
Example 8
Preparation of Poly{[N,N'-bis(2-hexyldecyl)-1,4,5,8-naphthalene
diimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2HD-T2)]
[0128] Preparation of P(NDI2HD-T2): Under argon, a mixture of
NDI2OD-Br.sub.2 (1.02 g, 1.17 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (0.58 g, 1.17 mmol),
Pd.sub.2dba.sub.3 (21.4 mg, 0.023 mmol), and P(o-tol).sub.3 (28.4
mg, 0.093 mmol) in anhydrous chlorobenzene (100 mL) was stirred at
90.degree. C. for 18 hours. Bromobenzene (2 mL) was then added and
the reaction mixture was maintained at 90.degree. C. for an
additional 14 hours. Upon cooling to room temperature, a solution
of KF (4 g) in water (8 mL) was added, and the resulting mixture
was stirred for 1 h. This reaction mixture was diluted with
chloroform (300 mL), and the resulting mixture was washed with
water (200 mL.times.3), dried over anhydrous Na.sub.2SO.sub.4, and
concentrated in vacuo. The residue was taken with chloroform (250
mL), and precipitated in methanol (300 mL) and acetone (300 mL) in
sequence. The resulting crude product was then subject to Soxhlet
extraction with methanol (15 h), acetone (24 h), and hexane (24 h).
The isolated solid product was dissolved in chloroform (600 mL),
and this solution was precipitated in methanol (600 mL). The
filtrate was collected by filtration, washed with methanol, and
dried in vacuum, leading to a dark blue solid (1.01 g, 98.1%).
.sup.1H NMR (CDCl.sub.2CDCl.sub.2, 500 MHz): .delta.: 8.50-8.80
(br, 2H), 7.37 (br, 4H), 4.13 (br, 4H), 2.00 (br, 2H), 1.20-1.60
(br, m, 48H), 0.87 (br, 12H). Elemental Analysis (calc. C, 73.93;
H, 8.27; N, 3.19). found C, 74.29; H, 8.31; N, 3.37. High
temperature GPC: Mn=16.7, Mw=55.4, PDI=3.3.
Example 9
Preparation of poly{[N,N'-bis(2-octyldodecyl)-3,4:9,10-perylene
diimide-(1,7 & 1,6)-diyl]-alt-5,5'-(2,2'-bithiophene)}
[P(PDI2OD-T2)]
[0129] Preparation of N,N'-bis(2-octyldodecyl)-(1,7 &
1,6)-dibromoperylene-3,4:9,10-bis(dicarboxiamide)
(PDI2OD-Br.sub.2): A mixture of PDA-Br.sub.2 (0.44 g, 0.80 mmol),
2-octyldodecylamine (0.71 g, 2.4 mmol), o-xylene (3 mL), and
propionic acid (1 mL) was stirred at 140.degree. C. for 2 hours.
Upon cooling to room temperature, most of the solvents were removed
in vacuo, and the residue was purified by column chromatography on
silica gel with a mixture of chloroform:hexane (1:1, v/v, slowly up
to 2:1) as eluent, affording a red solid as the product (0.63 g,
0.57 mmol, yield 71.5%). .sup.1H NMR (CDCl.sub.3 500 MHz): .delta.:
9.51 (d, J=8.0 Hz, 2H), 8.94 (s, 2H), 8.71 (d, J=8.0 Hz, 2H), 4.15
(d, J=7.0 Hz, 4H), 2.01 (m, 2H), 1.20-1.50 (m, 64H), 0.84-0.89 (m,
12H). Elemental Analysis (calc. C, 69.30; H, 8.00; N, 2.53). found
C, 69.42; H, 8.13; N, 2.61.
[0130] Preparation of
poly{[N,N'-bis(2-octyldodecyl)-3,4:9,10-perylene diimide-(1,7 &
1,6)-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(PDI2OD-T2)]: Under
argon, a mixture of PDI2OD-Br.sub.2 (113.9 mg, 0.103 mmol),
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (50.5 mg, 0.103 mmol),
and Pd(PPh.sub.3).sub.2Cl.sub.2 (3.1 mg, 0.004 mmol) in anhydrous
toluene (6 mL) was stirred at 90.degree. C. for 2 days.
Bromobenzene (0.2 mL) was then added and the reaction mixture was
maintained at 90.degree. C. for an additional 12 hours. Upon
cooling to room temperature, a solution of potassium fluoride (1 g)
in water (2 mL) was added. This mixture was stirred at room
temperature for 2 hours before it was diluted with chloroform (150
mL). The resulting mixture was washed with water (100 mL.times.3),
dried over anhydrous sodium sulfate, and concentrated on a rotary
evaporator. The residue was taken with chloroform (25 mL) and
precipitated in methanol (50 mL) and acetone (50 mL) in sequence.
The isolated dark solid was dissolved in chloroform (25 mL) and
heated to boil. Upon cooling to room temperature, the chloroform
solution was filtered through a 5 .mu.m filter, and the filtrate
was added slowly to methanol (50 mL). The precipitates were
collected by filtration, washed with methanol, and dried in vacuum,
leading to a deep blue solid as the product (105.0 mg, yield
91.5%). .sup.1H NMR (CDCl.sub.2CDCl.sub.2 500 MHz): .delta.: 8.72
(m, br, 2H), 8.40 (s, br, 4H), 7.12-7.45 (m, br, 4H), 4.11 (s, br,
4H), 2.01 (s, br, 2H), 1.15-1.50 (m, br, 64H), 0.84 (s, br, 12H).
GPC: M.sub.n=11.0K Da, M.sub.w=32.1K Da, PDI=2.9. Elemental
Analysis (calc. C, 77.65; H, 8.33; N, 2.52): fond C, 76.60; H,
7.94; N, 2.47.
Example 10
Preparation of dithienocoronene diimide-based copolymer
[P(DTC2OD-T2)]
[0131] Preparation of PDI2OD-T2Br2: A mixture of PDI2OD-T2 (1.95 g,
1.75 mmol) and NBS (1.12 g, 6.29 mmol) in dry DMF (100 mL) was
heated at 110.degree. C. for 17 hours under nitrogen. After cooling
to room temperature, the reaction mixture was evaporated to dryness
to give a semi-solid crude product. The crude product was initially
purified by column chromatography (silica gel,
dichloromethane:hexanes (2:1, v/v)) to give a mixture of 1,6 and
1,7 isomers which were separated after a second column
chromatography (silica gel, dichloromethane:hexanes (1:1), v/v)) to
yield pure 1,7 isomer as a deep purple solid (1.0 g, 45%
yield).
[0132] Preparation of DTC2OD-Br2: A mixture of PDI2OD-T2Br2 (347
mg, 0.272 mmol) and iodine (147 mg, 0.552 mmol) was dissolved in
benzene (200 mL), and exposed to the UV-light for 15 hours in a
Rayonet RPR-100 photochemical reactor equipped with sixteen RPR
3000 .ANG. lamps. After the photochemical reaction was done, the
precipitate was filtered and washed successively with methanol,
acetone and hexane, and dried in a vacuum oven (60.degree. C.,
overnight) to afford the pure compound as an orange solid (326 mg,
94% yield).
[0133] Preparation of P(DTC2OD-T2): The reagents
5,5'-bis(trimethylstannyl)-2,2'-bithiophene (11.6 mg, 0.024 mmol),
DTC2OD-Br2 (30 mg, 0.024 mmol), and Pd(PPh.sub.3).sub.2Cl.sub.2
(0.8 mg, 0.0012 mmol) in anhydrous toluene (4 mL) were heated at
90.degree. C. for 19 h under nitrogen in a sealed flask. After
cooling to room temperature, the dark green viscous reaction
mixture was poured into methanol (20 mL). After stirring for 2
hours, the precipitated dark solid was collected by gravity
filtration.
[0134] Preparation of Electron-Donor Polymers
Example 11
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl-(4-dodecyl-2-
,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithi-
ophene)2,6-diyl-(2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl-(2,5-t-
hiophenediyl)}] (x=0.23; y=0.77)
[0135] To a Schlenk flask were added
4,7-bis(5-bromo-2-thienyl)-2,1,3-benzothiadiazole (46.23 mg, 0.101
mmol),
4,8-bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[1,2-b:-
4,5-b']dithiophene (141.65 mg, 0.135 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-2,1,3-benzothiadiazole (24.6
mg, 0.0309 mmol), Pa.sub.2dba.sub.3 (4.93 mg, 0.00538 mmol), and
P(o-tol).sub.3 (13.10 mg, 0.431 mmol). The flask was degassed and
backfilled with nitrogen three times. Dry chlorobenzene (20 mL) was
injected and the reaction was heated to 130.degree. C. for 18
hours. The reaction was cooled to room temperature and the content
of the flask was poured into methanol (100 mL). The precipitates
were collected by filtration and the solids were extracted with
acetone for 1 hour, dichloromethane for 3 hours and chloroform for
three hours. Finally, the polymer was extracted with chlorobenzene.
The chloroform solution was poured into methanol, and the
precipitates were again collected by filtration, dried under vacuum
to afford the title polymer (40 mg).
Example 12
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxylbenzo[1,2-b:4,5-b']dithiophene)2,6-diyl-(-
3-dodecyl-2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl-(4-dodecyl-2,-
5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithio-
phene)-2,6-diyl-(2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl(2,5-th-
iophenediyl)}] (x=0.29; y=0.71)
[0136] To a Schlenk flask were added
4,8-bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[1,2-b:-
4,5-b']dithiophene (129.74 mg, 0.123 mmol),
4,7-bis(5-bromo-2-thienyl)-2,1,3-benzothiadiazole (39.53 mg, 0.0863
mmol), 4,7-bis(5-bromo-4-dodecyl-2-thienyl)-2,1,3-benzothiadiazole
(27.43 mg, 0.345 mmol), Pa.sub.2dba.sub.3 (4.513 mg, 0.000493
mmol), and P(o-tol).sub.3 (12.00 mg, 0.394 mmol). The flask was
degassed and backfilled with nitrogen three times. Dry
chlorobenzene (20 mL) was injected and the reaction was heated to
130.degree. C. for 18 hours. The reaction was cooled to room
temperature and the content of the flask was poured into methanol
(200 mL). The precipitates were collected by filtration and the
solids were extracted with ethyl acetate for 5 hours, and THF for 5
hours. Finally the polymer was extracted with chlorobenzene. The
chloroform solution was poured into methanol, and the precipitates
were again collected by filtration, dried under vacuum to afford
the title polymer (64 mg, 49% yield).
Example 13
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxylbenzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl-(4-dodecyl-2-
,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithi-
ophene)-2,6-diyl-(2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl(2,5-t-
hiophenediyl)}] (x=0.38; y=0.62)
[0137] To a Schlenk flask were added
4,8-bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[1,2-b:-
4,5-b']dithiophene (117.27 mg, 0.111 mmol),
4,7-bis(5-bromo-2-thienyl)-2,1,3-benzothiadiazole (30.62 mg, 0.0668
mmol), 4,7-bis(5-bromo-4-dodecyl-2-thienyl)-2,1,3-benzothiadiazole
(33.64 mg, 0.0423 mmol), Pa.sub.2dba.sub.3 (4.08 mg, 0.0045 mmol),
and P(o-tol).sub.3 (10.85 mg, 0.0356 mmol). The flask was degassed
and backfilled with nitrogen three times. Dry chlorobenzene (20 mL)
was injected and the reaction was heated to 130.degree. C. for 18
hours. The reaction was cooled to room temperature and the content
of the flask was poured into methanol (100 mL). The precipitates
were collected by filtration and the solids were extracted with
methanol for 8 hours, ethyl acetate for 5 hours, and then
dichloromethane for 15 hours. Finally the polymer was extracted
into chloroform. The chloroform solution was poured into methanol,
and the precipitates were again collected by filtration, dried
under vacuum to afford the title polymer 88 mg (72% yield).
Example 14
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl-(4-dodecyl-2-
,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxylbenzo[1,2-b:4,5-b']dithi-
ophene)-2,6-diyl-(2,5-thiophenediyl)-2,1,3-benzothiadiazole-4,7-diyl(2,5-t-
hiophenediyl)}] (x=0.5, v=0.5)
[0138] To a Schlenk flask were added
4,8-bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[1,2-b:-
4,5-b']dithiophene (600 mg, 0.60 mmol),
4,7-bis(5-bromo-2-thienyl)-2,1,3-benzothiadiazole (137.9 mg, 0.301
mmol), 4,7-bis(5-bromo-4-dodecyl-2-thienyl)-2,1,3-benzothiadiazole
(229.60 mg, 0.289 mmol), Pa.sub.2dba.sub.3 (22.05 mg, 0.024 mmol),
and P(o-tol).sub.3 (58.63 mg, 0.193 mmol). The flask was degassed
and backfilled with argon three times. Dry chlorobenzene (90 mL)
was injected and the reaction was heated to 130.degree. C. for 18
hours. The reaction was cooled to room temperature and the content
of the flask was poured into methanol (200 mL). The precipitates
were collected by filtration and the solids were extracted with
methanol for 5 hours, ethyl acetate for 5 hours, hexanes for 15
hours, and then dichloromethane for 5 hours. Finally the polymer
was extracted into chloroform. The chloroform solution was poured
into methanol, and the precipitates were again collected by
filtration, dried under vacuum to afford the title polymer 511 mg
(75% yield).
Example 15
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diy-
l-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxylbenzo[1,2--
b:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,-
5]thiadiazole-4,7-diyl(2,5-thiophenediyl)}] (x=0.5; v=0.5)
[0139]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]-
thiadiazole (20.77 mg, 0.025 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadiazole
(12.35 mg, 0.025 mmol),
4,8-bis-(2-hexyl-decyloxy)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']-
dithiophene (52.3 mg, 0.055 mmol), Pd.sub.2(dba).sub.3 (1.83 mg,
2.0 mol), and P(o-Tol).sub.3 (2.43 mg, 8.0 mol) were combined in a
50-mL flask. The system was purged with argon before 10 mL of
anhydrous chlorobenzene was added. The reaction mixture was heated
at 130.degree. C. for 18 hours. After cooling down to room
temperature, the polymer was precipitated out from methanol and
further purified using Soxhlet extraction with methanol, ethyl
acetate, and dichloromethane. The product was extracted with
chloroform and weighed 16.0 mg (27.5% yield) after removal of the
solvent and being dried in vacuo.
Example 16
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diy-
l(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis(2-hexyldecyl)oxylbenzo[1,2-b:-
4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]-
thiadiazole-4,7-diyl(2,5-thiophenediyl)}] (x=0.6; v=0.4)
[0140]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]-
thiadiazole (24.92 mg, 0.03 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadiazole
(9.88 mg, 0.02 mmol),
4,8-bis-(2-hexyl-decyl)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']dit-
hiophene (52.3 mg, 0.055 mmol), Pd.sub.2(dba).sub.3 (1.83 mg, 2.0
.mu.mol), and P(o-Tol).sub.3 (2.43 mg, 8.0 .mu.mol) were combined
in a 50-mL flask. The system was purged with argon before 10 mL of
anhydrous chlorobenzene was added. The reaction mixture was heated
at 131.degree. C. for 18 hours. After cooling down to room
temperature, the polymer was precipitated out from 150 ml of
methanol and further purified by Soxhlet extraction with methanol,
acetone, hexane, ethyl acetate, and dichloromethane. The product
was extracted with chloroform and weighed 38.0 mg (64.0% yield)
after removal of the solvent and being dried in vacuo.
Example 17
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diy-
l-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis(2-hexyldecyl)oxylbenzo[1,2-b-
:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5-
]thiadiazole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.7; v=0.3)
[0141]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]-
thiadiazole (29.08 mg, 0.035 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadiazole
(7.413 mg, 0.015 mmol),
4,8-bis-(2-hexyl-decyloxy)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']-
dithiophene (52.3 mg, 0.055 mmol), Pd.sub.2(dba).sub.3 (1.83 mg,
2.0 mol), and P(o-Tol).sub.3 (2.43 mg, 8.0 mol) were combined in a
50-mL flask. The system was purged with argon before 10 mL of
anhydrous chlorobenzene was added. The reaction mixture was heated
at 135.degree. C. for 18 hours. After cooling down to room
temperature, the polymer was precipitated out from methanol and
further purified using Soxhlet extraction with methanol, ethyl
acetate, dichloromethane. The product was extracted with chloroform
and weighed 48.0 mg (77.5% yield) after removal of the solvent and
being dried in vacuo.
Example 18
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diy-
l-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis(2-hexyldecyl)oxylbenzo[1,2-b-
:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5-
]thiadiazole-4,7-di-(2,5-thiophenediyl)}] (x=0.8; v=0.2)
[0142]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]-
thiadiazole (33.23 mg, 0.04 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadiazole
(4.94 mg, 0.01 mmol),
4,8-bis-(2-hexyl-decyloxy)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']-
dithiophene (52.3 mg, 0.055 mmol), Pd.sub.2(dba).sub.3 (1.83 mg,
2.0 .mu.mol), and P(o-Tol).sub.3 (2.43 mg, 8.0 .mu.mol) were
combined in a 50-mL flask. The system was purged with argon before
10 mL of anhydrous chlorobenzene was added. The reaction mixture
was heated at 135.degree. C. for 18 hours. After cooling down to
room temperature, the polymer was precipitated out from methanol
and further purified using Soxhlet extraction with methanol,
acetone, hexane, ethyl acetate, and dichloromethane. The product
was extracted with chloroform and weighed 36.0 mg (60% yield) after
removal of the solvent and being dried in vacuo.
Example 19
Preparation of
poly[{4,8-bis[(2-butyloctyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diy-
l-(4-dodecyl-2,5-thiophenediyl)}-co-{4,8-bis[(2-butyloctyl)oxy]benzo[1,2-b-
:4,5-b']dithiophene)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-benzo[1,2,5]th-
iadiazole-4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}] (x=0.5;
v=0.5)
[0143] The reagents
4,8-bis-(2-butyloctyloxy)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']d-
ithiophene (70 mg, 0.08 mmol),
4,7-bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadi-
azole (33.87 mg, 0.04 mmol),
4,7-bis-(5-bromo-4-dodecyl-thiophen-2-yl)-benzo[1,2,5]thiadiazole
(31.45 mg, 0.04 mmol), Pd.sub.2(dba).sub.3 (2.9 mg, 0.0032 mmol),
and P(o-tolyl).sub.3 (3.85 mg, 0.0127 mmol) in anhydrous
chlorobenzene (10 mL) were heated at 135.degree. C. for 16 h under
nitrogen in a sealed flask. After cooling to room temperature, the
dark purple viscous reaction mixture was poured into methanol (100
mL). The final precipitated polymer was collected by vacuum
filtration and dried in a vacuum oven to afford the polymer as a
black solid (83.3 mg, 87% yield).
Example 20
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiazole-4,7-diyl-(4--
dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-
-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiaz-
ole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.5; y=0.5)
[0144]
4,8-Bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[-
1,2-b:4,5-b']dithiophene (110 mg, 0.110 mmol),
4,7-bis(5-bromo-2-thienyl)-5-chloro-2,1,3-benzothiadiazole (27.18
mg, 0.0552 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-5-chloro-2,1,3-benzothiadiazole
(43.93 mg, 0.053 mmol), Pd.sub.2dba.sub.3 (4.04 mg, 0.00441 mmol),
and P(o-tol).sub.3 (10.75 mg, 0.0353 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (10 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hr. The reaction was cooled to room
temperature and the contents of the flask was poured into methanol
(100 mL). The precipitates were collected by filtration and the
solids were extracted with methanol for 3 hours, ethyl acetate for
3 hours, then dichloromethane for 18 hours. Finally the polymer was
extracted into chloroform. The chloroform solution was poured into
methanol, and the precipitates were again collected by filtration,
dried under vacuum to afford the polymer (94 mg, 72% yield).
Example 21
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiazole-4,7-diyl-(4--
dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-
-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiaz-
ole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.45; v=0.55)
[0145]
4,8-Bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[-
1,2-b:4,5-b']dithiophene (104.66 mg, 0.105 mmol),
4,7-bis(5-bromo-2-thienyl)-5-chloro-2,1,3-benzothiadiazole (27.10
mg, 0.055 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-5-chloro-2,1,3-benzothiadiazole
(37.32 mg, 0.045 mmol), Pd.sub.2dba.sub.3 (3.66 mg, 0.0042 mmol),
and P(o-tol).sub.3 (9.76 mg, 0.0336 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (20 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hr. The reaction was cooled to room
temperature and the contents of the flask was poured into methanol
(100 mL). The precipitates were collected by filtration and the
solids were extracted with methanol for 3 hours, ethyl acetate for
3 hours, then dichloromethane for 18 hours. Finally the polymer was
extracted into chloroform. The chloroform solution was poured into
methanol, and the precipitates again were collected by filtration,
then dried under vacuum to afford the polymer (102 mg, 86.4%
yield).
Example 22
Preparation of
poly[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiazole-4,7-diyl-(4--
dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[(2-hexyldecyl)oxy]benzo[1,2-b:4,5-
-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiaz-
ole-4,7-diyl-(2,5-thiophenediyl)}](x=0.4; v=0.6)
[0146]
4,8-Bis[(2-hexyldecyl)oxy]-2,6-bis(1,1,1-trimethyl-stannanyl)benzo[-
1,2-b:4,5-b']dithiophene (104.66 mg, 0.105 mmol),
4,7-bis(5-bromo-2-thienyl)-5-chloro-2,1,3-benzothiadiazole (29.56
mg, 0.06 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-5-chloro-2,1,3-benzothiadiazole
(33.17 mg, 0.04 mmol), Pd.sub.2dba.sub.3 (3.66 mg, 0.0042 mmol),
and P(o-tol).sub.3 (9.76 mg, 0.0336 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (20 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hr. The reaction was cooled to room
temperature and the content of the flask was poured into methanol
(100 mL). The precipitates were collected by filtration and the
solids were extracted with methanol for 3 hours, ethyl acetate for
3 hours, then dichloromethane for 18 hours. Finally the polymer was
extracted into chlorobenzene. The chlorobenzene solution was poured
into methanol, and the precipitates again were collected by
filtration, then dried under vacuum to afford the polymer (81.7 mg,
76.3% yield).
Example 23
Preparation of
poly[{4,8-bis[(2-butyloctyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5,6-dichloro-benzo[1,2,5]thiadiazole-4,7-diy-
l-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[(2-butyloctyl)oxy]benzo[1,2--
b:4,5-b']dithiophene)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-benzo[1,2,5]t-
hiadiazole-4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}] (x=0.5;
y=0.5)
[0147] The reagents
4,8-bis-(2-butyloctyloxy)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']d-
ithiophene (60.0 mg, 0.068 mmol),
4,7-bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-dichloro-benzo[1,2,5]thiadi-
azole (29.3 mg, 0.034 mmol),
4,7-bis-(5-bromo-4-dodecyl-thiophen-2-yl)-benzo[1,2,5]thiadiazole
(26.9 mg, 0.034 mmol), Pd.sub.2(dba).sub.3 (2.5 mg, 0.0027 mmol),
and P(o-tolyl).sub.3 (3.3 mg, 0.011 mmol) in anhydrous
chlorobenzene (10 mL) were heated at 135.degree. C. for 16 hr under
nitrogen in a sealed flask. After cooling to room temperature, the
dark purple viscous reaction mixture was poured into methanol (100
mL). The final precipitated polymer was collected by vacuum
filtration and dried in a vacuum oven to afford the polymer as a
black solid (78 mg, 93.8% yield).
Example 24
Preparation of
poly[{4,8-bis[(2-butyloctyl)oxy]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl--
(3-dodecyl-2,5-thiophenediyl)-5-fluoro-benzo[1,2,5]thiadiazole-4,7-diyl-(4-
-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[(2-butyloctyl)oxy]benzo[1,2-b:4,-
5-b']dithiophene)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-benzo[1,2,5]thiad-
iazole-4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}] (x=0.5; v=0.5)
[0148]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5-fluoro-benzo[1,2,5]thia-
diazole (20.32 mg, 0.025 mmol),
4,7-bis-(5-bromo-4-dodecyl-thiophen-2-yl)-benzo[1,2,5]thiadiazole
(19.87 mg, 0.025 mmol),
4,8-bis-(2-butyl-octyl)-2,6-bis-trimethylstannanyl-benzo[1,2-b:4,5-b']dit-
hiophene (44.23 mg, 0.050 mmol), Pd.sub.2(dba).sub.3 (1.83 mg, 2.0
.mu.mol), and P(o-Tol).sub.3 (2.43 mg, 8.0 .mu.mol) were combined
in a 50-mL flask. The system was purged with argon before 10 mL of
anhydrous chlorobenzene was added. The reaction mixture was heated
at 132.degree. C. for 22 hours. After cooling down to room
temperature, the polymer was precipitated out from methanol and
further purified by Soxhlet extraction with methanol, ethyl
acetate, hexane, and dichloromethane. The product was extracted
with dichloromethane and weighed 43 mg (71.6% yield) after removal
of the solvent and drying in vacuo.
Example 25
Preparation of
poly[{4,8-bis[5-(2-hexyldecyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophen-
e)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiazole--
4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[5-(2-hexyldecyl)thiop-
hen-2-yl]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5-ch-
loro-2,1,3-benzothiadiazole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.45;
v=0.55)
[0149] Preparation of
4,8-bis-[5-(2-hexyldecyl)-thiophen-2-yl]-1,5-dithia-s-indacene:
2-(2-Hexyldecyl)thiophene (7.12 g, 0.013 mol) was added into 500 mL
flask. The system was vacuumed and backfilled with argon three
times before 250 mL of anhydrous THF was added. Butyl lithium (2.5
M in hexane, 8.8 mL, 0.022 mol) was added dropwise after the system
was cooled to 0.degree. C. for 30 minutes. The resulting mixture
was stirred at room temperature for 1.5 hours before 2.2 g of
1,5-dithia-s-indacene-4,8-dione (0.01 mol) was added in the flow of
argon. The mixture was heated at 60.degree. C. for 2 hours before
being cooled to room temperature. The solution of 9.5 g of
SnCl.sub.2 in 150 mL of 30% HCl was added slowly into the reaction
system. The mixture was heated at 60.degree. C. for another 3 hours
before being cooled to room temperature. Hexane (500 mL) was added
and the mixture was washed with saturated Na.sub.2CO.sub.3 solution
until no white solid was observed and then dried with MgSO.sub.4.
After the removal of solvent,
4,8-bis-[5-(2-hexyldecyl)-thiophen-2-yl]-1,5-dithia-s-indacene (5.0
g, yield 62.2%) was obtained by purification with chromatography
with hexane as eluent. 11H NMR (CDCl.sub.3, 500 MHz): .delta. 7.67
(d, 2H, J=5.5 Hz), .delta. 7.48 (d, 2H, J=5.5 Hz), .delta. 7.32 (d,
2H, J=3.5 Hz), .delta. 6.91 (d, 2H, J=3.5 Hz), .delta. 2.88 (d, 4H,
J=6.5 Hz), .delta. 1.76 (s, 2H), .delta. 1.38-1.32 (m, 48H),
.delta. 0.91 (m, 12H).
[0150] Preparation of
4,8-bis-[5-(2-hexyldecyl)-thiophen-2-yl]-2,6-bis-trimethylstannanyl-1,5-d-
ithia-s-indacene:
4,8-Bis-[5-(2-hexyldecyl)-thiophen-2-yl]-1,5-dithia-s-indacene
(2.06 g, 2.56 mmol) was added into 200 mL flask. The system was
vacuumed and backfilled with argon 3 times before 80 mL of
anhydrous THF was injected. n-Butyl lithium (2.5 M in hexane, 2.3
mL, 5.6 mmol) was added after the mixture was cooled to -78.degree.
C. The mixture was stirred at -78.degree. C. for 30 minutes and
then at room temperature for one more hour. The system was cooled
down to -78.degree. C. again before trimethyltin chloride (0.5 g,
2.5 mmol) was added in portions. Stirring was continued overnight
at room temperature. Hexane (200 mL) was added and the organic
layer was washed with 150 mL of water. The aqueous layer was
extracted with 100 mL of hexane twice. The combined organic layer
was dried over anhydrous Na.sub.2SO.sub.4. Removal of the solvent
under vacuum yielded a yellow liquid (2.2 g, 76.0% yield) as the
final product after drying in vacuo overnight. 11H NMR (CDCl.sub.3,
500 MHz): .delta. 7.57 (s, 2H), .delta. 7.21 (d, 2H, J=3.0 Hz),
.delta. 6.78 (d, 2H, J=3.5 Hz), .delta. 2.76 (d, 4H, J=6.5 Hz),
.delta. 1.62 (s, 2H), .delta. 1.26-1.19 (m, 48H), .delta. 0.76 (m,
12H), .delta. 0.29 (m, 18H).
[0151]
4,8-Bis-[5-(2-hexyldecyl)-thiophen-2-yl]-2,6-bis-trimethylstannanyl-
-1,5-dithia-s-indacene (118.5 mg, 0.105 mmol),
4,7-bis(5-bromo-2-thienyl)-5-chloro-2,1,3-benzothiadiazole (27.10
mg, 0.055 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-5-chloro-2,1,3-benzothiadiazole
(37.32 mg, 0.045 mmol), Pd.sub.2dba.sub.3 (3.66 mg, 0.0042 mmol),
and P(o-tol).sub.3 (9.76 mg, 0.0336 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (20 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hr. The reaction was cooled to room
temperature and the content of the flask was poured into methanol
(100 mL). The precipitates were collected by filtration and the
solids were extracted with methanol for 3 hours, ethyl acetate for
3 hours, then dichloromethane for 18 hours. Finally, the polymer
was extracted into chloroform. The chloroform solution was poured
into methanol, and the precipitates again were collected by
filtration, then dried under vacuum to afford the polymer (59 mg,
43.3% yield).
Example 26
Preparation of
poly[{4,8-bis[5-(2-hexyldecyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophen-
e)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiazole--
4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[5-(2-hexyldecyl)thiop-
hen-2-yl]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5-ch-
loro-2,1,3-benzothiadiazole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.35;
y=0.65)
[0152]
4,8-Bis-[5-(2-hexyldecyl)-thiophen-2-yl]-2,6-bis-trimethylstannanyl-
-1,5-dithia-s-indacene (118.5 mg, 0.105 mmol),
4,7-bis(5-bromo-2-thienyl)-5-chloro-2,1,3-benzothiadiazole (32.02
mg, 0.065 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-5-chloro-2,1,3-benzothiadiazole
(29.03 mg, 0.035 mmol), Pd.sub.2dba.sub.3 (3.66 mg, 0.0042 mmol),
and P(o-tol).sub.3 (9.76 mg, 0.0336 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (20 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hr. The reaction was cooled to room
temperature and the contents of the flask was poured into methanol
(100 mL). The precipitates were collected by filtration and the
solids were extracted with methanol for 3 hours, ethyl acetate for
3 hours, then dichloromethane for 18 hours. Finally, the polymer
was extracted into chloroform. The chloroform solution was poured
into methanol, and the precipitates again were collected by
filtration, then dried under vacuum to afford the polymer (110 mg,
84.9% yield).
Example 27
Preparation of
poly[{4,8-bis[5-(2-hexyldecyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophen-
e)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-5-chloro-2,1,3-benzothiadiazole--
4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[5-(2-hexyldecyl)thiop-
hen-2-yl]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-5-ch-
loro-2,1,3-benzothiadiazole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.3;
v=0.7)
[0153]
4,8-Bis-[5-(2-hexyldecyl)-thiophen-2-yl]-2,6-bis-trimethylstannanyl-
-1,5-dithia-s-indacene (118.5 mg, 0.105 mmol),
4,7-bis(5-bromo-2-thienyl)-5-chloro-2,1,3-benzothiadiazole (34.49
mg, 0.07 mmol),
4,7-bis(5-bromo-4-dodecyl-2-thienyl)-5-chloro-2,1,3-benzothiadiazole
(24.88 mg, 0.03 mmol), Pa.sub.2dba.sub.3 (3.66 mg, 0.0042 mmol),
P(o-tol).sub.3 (4.86 mg, 0.0336 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (20 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hr. The reaction was cooled to rt
and the contents of the flask was poured into methanol (100 mL).
The precipitates were collected by filtration and the solids were
extracted with methanol for 3 hr, ethyl acetate for 3 hr,
dichloromethane for 18 hr. Finally the polymer was extracted into
chloroform. The chloroform solution was poured into methanol, and
the precipitates were again collected by filtration, dried under
vacuum to afford the polymer (70.0 mg, 61.3%).
Example 28
Preparation of
poly[{4,8-bis[5-(2-hexyldecyl)thiophen-2-yllbenzo[1,2-b:4,5-b']dithiophen-
e)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-5,6-difluoro-benzo[1,2,5]thiadia-
zole-4,7-diyl-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[5-(2-hexyldecyl)-
thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-
-5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diyl-(2,5-thiophenediyl)}]
(x=0.5; v=0.5)
[0154]
4,8-Bis-[5-(2-hexyldecyl)-thiophen-2-yl]-2,6-bis-trimethylstannanyl-
-1,5-dithia-s-indacene (118.5 mg, 0.105 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadiazole
(24.71 mg, 0.050 mmol),
4,7-bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5,6-difluoro-benzo[1,2,5]thiadi-
azole (41.54 mg, 0.050 mmol), Pa.sub.2dba.sub.3 (3.66 mg, 0.0042
mmol), P(o-tol).sub.3 (9.76 mg, 0.0336 mmol) were placed in a
Schlenk flask. The flask was degassed and backfilled with argon
three times. Dry chlorobenzene (20 mL) was injected and the
reaction was heated to 130.degree. C. for 18 hr. The reaction was
cooled to rt and the contents of the flask was poured into methanol
(100 mL). The precipitates were collected by filtration and the
solids were extracted with methanol for 3 hr, ethyl acetate for 3
hr, dichloromethane for 18 hr. Finally the polymer was extracted
into chloroform. The chloroform solution was poured into methanol,
and the precipitates were again collected by filtration, dried
under vacuum to afford the polymer (52.0 mg, 39.5%).
Example 29
Preparation of
poly[{2,6-(4,8-didodecylbenzo[1,2-b:4,5-b']dithiophene)}-alt-{5,5-(1,4-bi-
s(2-butyloctyl)-3,6-dithiophen-2-yl-1,4-dihydropyrrolo[3,2-b]pyrrole-2,5-d-
ione)}
[0155] To a 10 mL microwave tube,
2,6-bis(trimethylstannyl)-4,8-didodecylbenzo[1,2-b:4,5-b'
]dithiophene (51.2 mg, 60 mol),
3,6-bis-(5-bromo-thiophen-2-yl)-1,4-bis-(2-butyloctyl)-1,4-dihydropyrrolo-
[3,2-b]pyrrole-2,5-dione (47.7 mg, 60 mol), Pd.sub.2(dba).sub.3
(2.7 mg, 5 mol %) and tri(o-tolyl)phosphine (3.7 mg, 20 mol %) were
mixed in anhydrous toluene (5 mL) under argon. Then the tube was
heated to 180.degree. C. in 30 minutes and kept at this temperature
for 270 minutes by a CEM Discover Microwave reactor. After cooling,
it was poured into MeOH (50 mL), filtered and dried in a vacuum
oven to give a dark brown solid (68.4 mg). Using a Soxhlet setup,
the crude product was extracted successively, with MeOH, hexane,
ethyl acetate, THF and chloroform. The chloroform extract was
poured into MeOH (100 mL) and the solid was collected. Finally, a
dark brown solid (62.1 mg, yield 89%, Mn=792 kDa, d=2.7) was
obtained. Elemental Analysis: Calcd. C, 74.56; H, 9.21; N, 2.42.
Found: C, 74.42; H, 9.18; N, 2.55.
Example 30
Preparation of
poly[{2,6-(4,8-bis(2-ethylhexyl)benzo[1,2-b:4,5-b']dithiophene)}-alt-{5,5-
-(1,4-bis(2-butyloctyl)-3,6-dithiophen-2-yl-1,4-dihydropyrrolo[3,2-b]pyrro-
le-2,5-dione)}]
[0156] To a 10 mL microwave tube,
2,6-bis(trimethylstannyl)-4,8-bis(2-ethylhexyl)[1,2-b:4,5-b']dithiophene
(44.4 mg, 60 mol),
3,6-bis-(5-bromo-thiophen-2-yl)-1,4-bis-(2-butyloctyl)-1,4-dihydropyrrolo-
[3,2-b]pyrrole-2,5-dione (47.7 mg, 60 mol), Pd.sub.2(dba).sub.3
(2.7 mg, 5 mol %) and tri(o-tolyl)phosphine (3.7 mg, 20 mol %) were
mixed in anhydrous toluene (5 mL) under argon. Then the tube was
heated to 180.degree. C. in 30 minutes and kept at this temperature
for 270 minutes by a CEM Discover Microwave reactor. After cooling,
it was poured into MeOH (50 mL), filtered and dried in a vacuum
oven to give a dark brown solid (61.0 mg). Using a Soxhlet setup,
the crude product was extracted successively with MeOH, hexane,
ethyl acetate, THF and chloroform. The chloroform extract was
poured into MeOH (100 mL) and the solid was collected. Finally, a
dark brown solid (54.0 mg, yield 86%, Mn=26 kDa, d=27) was
obtained. Elemental Analysis: Calcd. C, 73.37; H, 8.66; N, 2.67.
Found: C, 73.06; H, 8.50; N, 2.80.
Example 31
Preparation of
poly[{2,6-(4,8-bis(2-ethylhexyl)benzo[1,2-b:4,5-b']dithiophene)}-alt-{5,5-
-(1,4-bis(2-butyloctyl)-3,6-dithiophen-2-yl-1,4-dihydropyrrolo[3,2-b]pyrro-
le-2,5-dione)}]
[0157] To a 10 mL microwave tube,
2,6-bis(trimethylstannyl)-4,8-didodecyloxybenzo[1,2-b:4,5-b']dithiophene
(53.1 mg, 60 mol),
3,6-bis-(5-bromo-thiophen-2-yl)-1,4-bis-(2-butyloctyl)-1,4-dihydropyrrolo-
[3,2-b]pyrrole-2,5-dione (47.7 mg, 60 mol), Pd.sub.2(dba).sub.3
(2.7 mg, 5 mol %) and tri(o-tolyl)phosphine (3.7 mg, 20 mol %) were
mixed in anhydrous toluene (5 mL) under argon. Then the tube was
heated to 180.degree. C. in 30 minutes and kept at this temperature
for 270 minutes by a CEM Discover Microwave reactor. After cooling,
it was poured into MeOH (50 mL), filtered and dried in a vacuum
oven to give a dark brown solid. Using a Soxhlet setup, the crude
product was extracted successively with MeOH, hexane, ethyl
acetate, ether and dichloromethane. The dichloromethane extract was
poured into MeOH (100 mL) and the solid was collected. Finally, a
dark brown solid (45.0 mg, yield 63%, Mn=49 kDa, d=30) was
obtained. Elemental Analysis: Calcd. C, 72.55; H, 8.96; N, 2.35.
Found: C, 72.28; H, 8.85; N, 2.48.
Example 32
Preparation of
poly[{4,8-bis[5-(2-hexyldecyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophen-
e)-2,6-diyl-(3-dodecyl-2,5-thiophenediyl)-benzo[1,2,5]thiadiazole-4,7-diyl-
-(4-dodecyl-2,5-thiophenediyl)}-co-[{4,8-bis[5-(2-hexyldecyl)thiophen-2-yl-
]benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-(2,5-thiophenediyl)-benzo[1,2,5]-
thiadiazole-4,7-diyl-(2,5-thiophenediyl)}] (x=0.5; v=0.5)
[0158]
4,8-Bis-[5-(2-hexyl-decyl)-thiophen-2-yl]-2,6-bis-trimethylstannany-
l-1,5-dithia-s-indacene (118.5 mg, 0.105 mmol),
4,7-bis(5-bromo-2-thienyl)-2,1,3-benzothiadiazole (22.91 mg, 0.05
mmol), 4,7-bis(5-bromo-4-dodecyl-2-thienyl)-2,1,3-benzothiadiazole
(39.74 mg, 0.05 mmol), Pa.sub.2dba.sub.3 (3.66 mg, 0.004 mmol),
P(o-tol).sub.3 (4.86 mg, 0.016 mmol) were placed in a Schlenk
flask. The flask was degassed and backfilled with argon three
times. Dry chlorobenzene (20 mL) was injected and the reaction was
heated to 130.degree. C. for 18 hours. The reaction was cooled to
room temperature and the contents of the flask were poured into
methanol (100 mL). The precipitates were collected by filtration
and the solids were extracted with methanol for 6 hours, ethyl
acetate for 16 hours, and dichloromethane for 24 hours. Finally the
polymer was extracted into chloroform. The chloroform solution was
poured into methanol, and the precipitates were again collected by
filtration, dried under vacuum to afford the polymer (60.0 mg,
46.8%). Elemental Analysis: Found (%): C, 72.16; H, 8.18; N,
2.27.
Example 33
Preparation of
poly[{2,6-(4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:4,5-b']dithioph-
ene)}-alt-{5,5-(1,4-bisdecyl-3,6-dithiophen-2-yl-1,4-dihydropyrrolo[3,2-b]-
pyrrole-2,5-dione)}]
[0159] To a 100 mL storage vessel,
2,6-bis(trimethylstannyl)-4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:-
4,5-b']dithiophene (105.8 mg, 93.7 mol),
3,6-bis-(5-bromo-thiophen-2-yl)-1,4-bisdecyl-1,4-dihydropyrrolo[3,2-b]pyr-
role-2,5-dione (69.2 mg, 93.7 mol), Pd.sub.2(dba).sub.3 (4.3 mg, 5
mol %) and tri(o-tolyl)phosphine (5.7 mg, 20 mol %) were mixed in
anhydrous chlorobenzene (8 mL) under argon. Then the tube was
heated at 135.degree. C. for 16 hours. After cooling, it was poured
into MeOH (50 mL), filtered and dried in a vacuum oven. Using a
Soxhlet setup, the crude product was extracted successively with
MeOH, ethyl acetate, dichloromethane, and chloroform. The
chloroform extract was poured into MeOH (100 mL) and the solid was
collected. Finally, a dark blue solid (76 mg, yield 59%, high
temperature GPC in trichlorobenzene: Mn=21.6 kDa, d=1.97) was
obtained. Elemental Analysis: Calcd. C, 73.10; H, 8.62; N, 2.03.
Found: C, 72.83; H, 8.51; N, 2.12.
Example 34
Preparation of Naphthodithiophene-Based Donor Polymer
[0160] Naphthalene-2,6-diol (16.0 g, 0.1 mol) and NaH (6.0 g, 0.25
mol) was combined together in a 500 mL flask under argon. The
mixture was cooled to -78.degree. C. before the addition of
anhydrous DMF (200 mL) by injection. The mixture emitted a
significant amount of gas. Stirring was continued at room
temperature for 2 hours. Dimethyl sulfate (31.5 g, 0.25 mol) was
added dropwise after the mixture was cooled to -78.degree. C.
again. The reaction was continued overnight at room temperature
before 200 mL of anhydrous DMF was added. 2,6-Dimethoxy-naphthalene
(16.0 g, .about.85.1% yield) was collected as a white powder by
filtration and washed with water and methanol before drying under
vacuum. 1H NMR (CDCl.sub.3, 500 MHz): .delta. 7.67 (d, 2H, J=8.5
Hz), .delta. 7.17 (d.times.d, 2H, J=8.5 Hz.times.2.5 Hz), .delta.
7.13 (d, 2H, J=2.5 Hz), .delta. 7.13 (d, 2H, J=2.5 Hz), .delta.
3.93 (s, 6H).
[0161] To a 200 mL Schlenk flask, 2,6-dimethoxy-naphthalene (3.76
g, 20.0 mmol) was added. The system was vacuumed and backfilled
with argon 3 times before 100 mL of anhydrous THF was added. After
the mixture was cooled to 0.degree. C. for 30 minutes,
n-butyllithium (34 mL, 2.5 M, 85.0 mmol) was injected dropwise. The
resulting mixture was stirred at room temperature for 4 hours
before being cooled to -78.degree. C.
2-(2,2-Diethoxy-ethyldisulfanyl)-1,1-diethoxyethane (26.6 g, 103
mmol) was injected in one portion. The dry ice bath was removed 5
minutes later and the mixture was stirred overnight. Water (100 mL)
was added to quench the reaction and the mixture was stirred at
room temperature for 10 minutes. Hexane (150 mL.times.3) was used
to extract the product and the combined organic layer was dried
with anhydrous Na.sub.2SO.sub.4. Methanol (150 mL) was added and
2,6-bis-(2,2-diethoxy-ethylsulfanyl)-3,7-dimethoxy-naphthalene (5.0
g, .about.52.0% yield) as a yellow solid was collected by
filtration and washed with methanol and dried under vacuum. .sup.1H
NMR (CDCl.sub.3, 500 MHz): .delta. 7.62 (s, 2H), .delta. 7.00 (s,
2H), .delta. (t, 2H, J=2.5 Hz), .delta. 3.99 (s, 6H), .delta. 3.73
(m, 4H), .delta. 3.60 (m, 4H), .delta. 3.23 (d, 4H, J=2.5 Hz),
.delta. 1.23 (t, 12H, J=9.0 Hz).
[0162]
2,6-Bis-(2,2-diethoxy-ethylsulfanyl)-3,7-dimethoxy-naphthalene (5.0
g, 10.3 mmol) and 6.8 g of 84% polyphorphoric acid were added into
a 250 mL 3-neck flask equipped with a condenser. The system was
flashed with argon for 15 minutes before 50 mL of anhydrous
chlorobenzene was added. The mixture was heated at 140.degree. C.
for 40 hours before it was cooled down to room temperature.
Dichloromethane (100 mL) was added. The organic mixture was washed
with saturated NaHCO.sub.3 before the solvent was removed under
vacuum. Methanol (100 mL) was added before
5,10-dimethoxy-1,6-dithia-dicyclopenta[a,f]naphthalene (2.0 g,
.about.66% yield) was collected as a white solid by filtration,
washed with methanol and dried in vacuo. .sup.1H NMR (CDCl.sub.3,
500 MHz): .delta. 7.97 (d, 2H, J=5.5 Hz), .delta. 7.62 (d, 2H,
J=5.5 Hz), .delta. 7.51 (s, 2H), .delta. 4.18 (s, 6H).
[0163] 5,10-Dimethoxy-1,6-dithia-dicyclopenta[a,f]naphthalene (1.80
g, 6.0 mmol), 1.14 g (6.0 mmol) of toluene-4-sulfonic acid
(CH.sub.3C6H.sub.4SO.sub.3H'H.sub.2O), and 35 mL of 2-butyloctanol
were added into a 250 mL 3-neck flask equipped with a condenser.
The system was heated at 180.degree. C. overnight under argon
before the mixture was cooled down to room temperature. Hexane (200
mL) was added and the organic layer was washed with saturated
NaHCO.sub.3 before the solvent was removed under vacuum. Excess
2-butyloctanol was distilled out under vacuum. Column
chromatography (silica gel) with an eluent of
hexane/dichloromethane (v/v, 100/4) yielded product
5,10-bis-(2-butyl-octyloxy)-1,6-dithia-dicyclopenta[a,f]naphthalene
as a colorless liquid (2.5 g, .about.68.5% yield). .sup.1H NMR
(CDCl.sub.3, 500 MHz): .delta. 7.96 (d, 2H, J=5.5 Hz), .delta. 7.60
(d, 2H, J=5.5 Hz), .delta. 7.50 (s, 2H), .delta. 4.23 (d, 4H, J=5.5
Hz), .delta. 1.99 (m, 2H), .delta. 1.33 (m, 32H), .delta. 0.96 (t,
6H, J=7.0 Hz), .delta. 0.90 (t, 6H, J=7.0 Hz).
[0164]
5,10-Bis-(2-butyl-octyloxy)-1,6-dithia-dicyclopenta[a,f]naphthalene
(1.41 g, 2.3 mmol) was added into a 200 mL flask. The system was
vacuumed and backfilled with argon 3 times before 60 mL of
anhydrous THF was injected. N-Butyllithium (2.2 mL, 2.5 M in
hexane, 5.09 mmol) was added after the mixture was cooled to
-78.degree. C. A white precipitate was observed after the mixture
was stirred at -78.degree. C. for 30 minutes. Stirring was
continued at room temperature for one more hour before the mixture
was cooled down to -78.degree. C. again. Trimethyltin chloride
(1.20 g, 5.75 mmol) was added in portions and stirring was
continued overnight at room temperature. Hexane (100 mL) was added
and the organic layer was washed with 150 mL of water. The aqueous
layer was extracted with 100 mL of hexane twice. The combined
organic layer was dried over anhydrous Na.sub.2SO.sub.4. Removal of
solvent under vacuum yielded a white solid. The colorless
crystalline product,
5,10-bis-(2-butyl-octyloxy)-2,7-bis-trimethylstannanyl-1,6-dithia-dicyclo-
penta[a,f]naphthalene, (1.70 g, .about.79% yield) was obtained
after recrystallization from a hexane/iso-propanol mixture. .sup.1H
NMR (CDCl.sub.3, 500 MHz): .delta. 7.80 (s, 2H), .delta. 7.69 (s,
2H), .delta. 4.25 (d, 4H, J=5.5 Hz), .delta. 1.99 (m, 2H), .delta.
1.33 (m, 32H), .delta. 0.96 (t, 6H, J=7.0 Hz), .delta. 0.90 (t, 6H,
J=7.0 Hz), .delta. 0.51 (m, 18H).
[0165]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)benzo[1,2,5]thiadiazole
(47.69 mg, 0.06 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)benzo[1,2,5]thiadiazole (9.16 mg,
0.02 mmol), and
5,10-bis-(2-butyl-octyloxy)-2,7-bis-trimethylstannanyl-1,6-dithia-dicyclo-
penta[a,f]naphthalene (74.77 mg, 0.08 mmol), Pd.sub.2(dba).sub.3
(2.93 mg, 3.2 .mu.mol), P(o-Tol).sub.3 (3.90 mg, 12.8 .mu.mol) were
combined in a 50 mL flask. The system was purged with argon before
16 mL of anhydrous chlorobenzene was added. The reaction mixture
was heated at 135.degree. C. for 18 hours. After cooling down to
room temperature, the polymer was precipitated out from 80 ml of
methanol and further purified by a Soxlet apparatus with methanol,
ethyl acetate, dichloromethane. The residue weighed 49.0 mg
(.about.81.6% yield) after removing the solvent and drying in
vacuo.
Example 35
Preparation of Naphthodithiophene-Based Donor Polymer
[0166]
4,7-Bis-(5-bromo-4-dodecyl-thiophen-2-yl)-5-chloro-benzo[1,2,5]thia-
diazole (49.76 mg, 0.06 mmol),
4,7-bis-(5-bromo-thiophen-2-yl)-5-chloro-benzo[1,2,5]thiadiazole
(9.85 mg, 0.02 mmol),
5,10-bis-(2-butyl-octyloxy)-2,7-bis-trimethylstannanyl-1,6-dithia-dicyclo-
penta[a,f]naphthalene (74.77 mg, 0.08 mmol), Pd.sub.2(dba).sub.3
(2.93 mg, 3.2 .mu.mol), and P(o-Tol).sub.3 (3.90 mg, 12.8 .mu.mol)
were combined in a 50 mL flask. The system was purged with argon
before 16 mL of anhydrous chlorobenzene was added. The reaction
mixture was heated at 135.degree. C. for 18 hours. After cooling
down to room temperature, the polymer was precipitated out from 80
ml of methanol and further purified by a Soxlet apparatus with
methanol, ethyl acetate, and dichloromethane. The residue weighed
83.0 mg (.about.86.9% yield) after removing the solvent and drying
in vacuo.
Example 36
Preparation of
2,6-bis(trimethylstannyl)-benzo[1,2-b:4,5-b']dithiophene-4,8-(5-(2-hexyld-
ecyl)-2-thiophenecarboxylic acid) ester
##STR00074## ##STR00075##
[0167] 1-Iodo-2-hexyldecane (1)
[0168] Under air, triphenylphosphine (107.44 g, 410 mmol, 1.19
equiv.) and imidazole (28.9 g, 424 mmol, 1.23 equiv.) were
dissolved in dichloromethane (800 mL). 2-Hexyl-1-decanol (100 mL,
345 mmol., 1.00 equiv.) was added to the solution, and the reaction
mixture was cooled to 0.degree. C. Iodine (103.6 g, 408 mmol., 1.18
equiv.) was added portion-wise over 1 hour, after which the
suspension was stirred at 0.degree. C. for an additional hour, and
then at ambient temperature for 18 hours. The mixture was quenched
with saturated aqueous Na.sub.2SO.sub.3 (150 mL), and DCM was
removed in vacuo. Hexane (200 mL) was added to the residue, and the
mixture was filtered to remove salts that had precipitated. The
organic material was extracted with hexanes (3.times.300 mL), dried
over Na.sub.2SO.sub.4, filtered through a pad of silica gel, and
then concentrated in vacuo to give a clear, colorless oil (97.8 g,
82% yield). .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 3.28 (d,
J=4.6 Hz, 2H), 1.34-1.19 (m, 24H), 1.12 (b, 1H), 0.91-0.87 (m,
6H).
2-(2-Hexyldecyl)thiophene (2)
[0169] A solution of thiophene (46.4 g, 551 mmol., 2.50 equiv.) and
THF (300 mL) was cooled to -78.degree. C. n-Butyllithium (2.5 M in
hexanes, 212 mL, 528 mmol., 2.40 equiv.) was added over 1 hour. The
mixture was stirred for an additional 30 minutes at -78.degree. C.
before a solution of 1-iodo-2-hexyldecane (90.0 g, 220 mmol., 1.00
equiv) in THF (200 mL) was added slowly over 1 hour. After stirring
for 1 hour at -78.degree. C., the reaction mixture was warmed to
ambient temperature and stirred for 18 hours. Water (200 mL) was
added and the organic material was extracted with Et.sub.2O
(3.times.250 mL), washed with additional water, dried over
Na.sub.2SO.sub.4, filtered, and concentrated in vacuo. The
resulting brown residue was purified by silica gel column
chromatography (hexanes) to give a pale yellow oil (52.03 g, 77%
yield). .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.12 (dd, J=5.2,
1.2 Hz, 1H), 6.92 (m, 1H), 6.76 (dd, J=3.4, 0.9 Hz, 1H), 2.76 (d,
J=6.7, 2H), 1.62 (b, 1H), 1.33-1.21 (m, 24H), 0.91-0.87 (m,
6H).
5-(2-Hexyldecyl)-2-thiophenecarboxylic acid (3)
[0170] 2-(2-Hexyldecyl)thiophene (1.00 g, 3.24 mmol., 1.00 equiv.)
and THF (24 mL) were added to a 50 mL schlenk flask. The solution
was cooled to 0.degree. C. n-Butyllithium (2.5 M in hexanes, 1.36
mL, 1.05 equiv.) was then added over 2 minutes. The solution was
stirred for 1 hour at 0.degree. C., then the ice/water bath was
removed and the solution was stirred for 20 minutes at ambient. The
solution was cooled back to 0.degree. C. and carbon dioxide
(obtained by subliming dry ice submerged in THF in a separate flask
placed in a 25.degree. C. heat bath) was bubbled through the
solution for 30 minutes. The solution was diluted with 1 N
hydrochloric acid (50 mL) and EtOAc (50 mL). The organic layer was
washed with brine, dried with MgSO.sub.4, and concentrated.
Purification by silica gel column chromatography (4:1
hexanes-EtOAc, 2% AcOH) gave a colorless liquid (1.086 g, 95%
yield). .sup.1H NMR (500 MHz, CDCl.sub.3) .delta. 7.74 (d, J=3.8
Hz, 1H), 6.80 (d, J=3.8 Hz, 1H), 2.79 (d, J=6.8, 2H), 1.67 (b, 1H),
1.34-1.21 (m, 24H), 0.91-0.87 (m, 6H).
5-(2-Hexyldecyl)-2-thiophenecarbonyl chloride (4)
[0171] 5-(2-Hexyldecyl)-2-thiophenecarboxylic acid (1.00 g, 2.84
mmol., 1.00 equiv.) and CH.sub.2Cl.sub.2 (5 mL) were added to a 10
mL schlenk flask. The solution was cooled to 0.degree. C. Oxalyl
chloride (0.60 mL, 6.5 mmol, 2.3 equiv.) was then added. The
ice/water bath was left in place and the solution was stirred for
64 hours while warming to room temperature. The reaction mixture
was concentrated to a clear brown liquid (931 mg, 88% yield).
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.84 (d, J=3.9 Hz, 1H),
6.87 (d, J=3.8 Hz, 1H), 2.81 (d, J=6.7, 2H), 1.68 (b, 1H),
1.34-1.19 (m, 24H), 0.93-0.85 (m, 6H).
4,8-Dimethoxy-benzo[1,2-b:4,5-b']dithiophene (5)
[0172] Benzo[1,2-b:4,5-b']dithiophene-4,8-dione (7.50 g, 34.0
mmol., 1.00 equiv.), ethanol (45 mL) and water (45 mL) were added
to a 250 mL 2-neck round-bottom flask fitted with a reflux
condenser. NaBH.sub.4 (3.89 g, 102 mmol., 3.00 equiv.) was then
added portion-wise cautiously. The reaction mixture was heated to
reflux for 1 hour. The flask was removed from the heat bath and
potassium hydroxide (4.39 g, 78.2 mmol., 2.30 equiv.) was added
slowly to the reaction mixture with vigorous stirring. The
suspension was stirred at reflux for 30 minutes before adding
dimethyl sulfate (16 mL, 170 mmol., 5.0 equiv.), and the suspension
was refluxed for 64 hours. The reaction mixture was cooled to room
temperature and diluted with water (75 mL) and diethyl ether (500
mL) and more water (300 mL). The organic layer was washed with
brine (200 mL), dried with MgSO.sub.4 and concentrated. The crude
material was purified by silica gel column chromatography (solid
loading, gradient of 1:1 to 1:2 hexanes-dichloromethane) to give a
white solid (5.314 g, 62% yield). .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.52 (d, J=5.5 Hz, 2H), 7.41 (d, J=5.5 Hz, 2H), 2.81 (d,
J=6.7, 2H), 4.15 (s, 6H).
2,6-Dibromo-4,8-dimethoxy-benzo[1,2-b:4,5-b']dithiophene (6)
[0173] 4,8-Dimethoxy-benzo[1,2-b:4,5-b']dithiophene (1.00 g, 3.99
mmol., 1.00 equiv.) and THF (44 mL) were added to a 100 mL schlenk
flask and the mixture was cooled to -78.degree. C. n-Butyllithium
(2.5 M in hexanes, 3.5 mL, 8.8 mmol., 2.2 equiv.) was then added
and the mixture was stirred at -78.degree. C. for 15 minutes before
removing the dry ice/acetone bath and stirring at ambient for 30
minutes. The suspension was cooled to -78.degree. C. and carbon
tetrabromide (3.18 g, 9.59 mmol., 2.40 equiv.) was added. The dry
ice/acetone bath was removed and the mixture was stirred at ambient
for 1 hour. Water and dichloromethane were added (brine was also
added to break emulsion) and the aqueous layer was extracted with
dichloromethane. The organic layer was washed with brine, dried
with MgSO.sub.4 and concentrated. The crude material was purified
by silica gel column chromatography (solid loading, 1:1
dichloromethane-hexane) and trituration in hexanes to give a beige
crystalline solid (1.368 g, 84% yield). .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 7.48 (s, 2H), 4.07 (s, 6H).
2,6-Dibromo-benzo[1,2-b:4,5-b']dithiophene-4,8-diol (7)
[0174] 2,6-Dibromo-4,8-dimethoxy-benzo[1,2-b:4,5-b']dithiophene
(500 mg, 1.22 mmol., 1.00 equiv.) and dichloromethane (12 mL) were
added to a 50 mL schlenk flask. The mixture was cooled to
-78.degree. C. and boron tribromide was added (1.0 M solution in
dichloromethane, 2.5 mL, 2.5 mmol., 2.1 equiv.) slowly. The mixture
was stirred for 15 minutes at -78.degree. C. before replacing the
dry/ice acetone bath with an ice/water bath. The reaction mixture
was left to warm to room temperature while stirring for 16 hours
before cooling to 0.degree. C. Water (dropwise at first, 150 mL
total) and additional dichloromethane (50 mL) were added. The
dichloromethane was removed on the rotary evaporator and the solid
was collected by filtration. The solid was washed with water (25
mL) and dichloromethane (25 ml) to give a pale blue/green crude
solid to be dried under vacuum and used in the next step without
additional purification (287 mg). .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 10.13 (s, 2H), 7.71 (s, 2H).
2,6-Dibromo-benzo[1,2-b:4,5-b']dithiophene-4,8-(5-(2-hexyldecyl)-2-thiophe-
necarboxylic acid) ester (8)
[0175] 2,6-Dibromo-benzo[1,2-b:4,5-b']dithiophene-4,8-diol (150 mg,
0.395 mmol., 1.00 equiv.), dichloromethane (6 mL) and triethylamine
(0.22 mL, 1.6 mmol, 4.0 equiv.) were added to a 25 mL 2-neck
round-bottom flask fitted with a reflux condenser. A solution of
5-(2-hexyldecyl)-2-thiophenecarbonyl chloride in dichloromethane (2
mL) was then added. The flask was placed in a 45.degree. C. heat
bath and the reaction mixture was stirred at reflux for 16 hours
before cooling to room temperature, diluting with dichloromethane
(60 mL) and washing with water (60 mL). The organic layer was dried
with MgSO.sub.4 and concentrated. The crude material was purified
by silica gel column chromatography (solid loading, 1:1
dichloromethane-hexanes) to give a white solid (266 mg, 40% yield
over two steps). m.p. 76.degree. C. .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 7.95 (d, J=3.7 Hz, 2H), 7.32 (s, 2H), 6.93 (d,
J=3.6 Hz, 2H), 2.87 (d, J=6.6, 4H), 1.74 (b, 2H), 1.40-1.21 (m,
48H), 0.94-0.85 (m, 12H). Anal. calcd. for
(C.sub.52H.sub.72O.sub.4S.sub.4): C, 59.53; H, 6.92. Found: C,
59.46; H, 6.80.
2,6-Bis(trimethylstannyl)-benzo[1,2-b:4,5-b']dithiophene-4,8-(5-(2-hexylde-
cyl)-2 thiophenecarboxylic acid) ester (9)
[0176]
2,6-Dibromo-benzo[1,2-b:4,5-b']dithiophene-4,8-(5-(2-hexyldecyl)-2--
thiophenecarboxylic acid) ester (150 mg, 0.143 mmol., 1.00 equiv.)
and THF (7 mL) were added to a 50 mL schlenk tube. The solution was
cooled to -78.degree. C. and n-butyllithium (2.5 M in hexanes, 126
.mu.L, 0.315 mmol., 2.2 equiv.) was added over 2 minutes. The
mixture was stirred at -78.degree. C. for 1 hour before adding
trimethyltin chloride (68 mg, 0.343 mmol., 2.40 equiv.). The dry
ice/acetone bath was removed and the reaction was stirred at
ambient for 2 hours before diluting with water (30 mL) and diethyl
ether (50 mL). The organic layer was washed with water (30 mL) and
brine (30 mL), dried with MgSO.sub.4 and concentrated to a yellow
crude oil (101 mg), which was used in the polymerization step
without further purification. .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.99 (d, J=3.7 Hz, 2H), 7.34 (s, 2H), 6.93 (d, J=3.6 Hz,
2H), 2.88 (d, J=6.4, 4H), 1.75 (b, 2H), 1.40-1.20 (m, 48H),
0.93-0.85 (m, 12H), 0.48-0.32 (m, 18H).
Example 37
Preparation of Chlorinated Repeating Units
[0177] Chlorinated repeating units can be prepared according to the
schemes below.
[0178] a) Repeating units comprising 3- or 4-chlorinated thienyl
groups:
##STR00076## ##STR00077##
[0179] b) Repeating units comprising 3,7-dichlorinated
benzo[1,2-b:4,5-b']dithienyl groups:
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
##STR00083##
[0180] See, e.g., Maruire et al., J. Med. Chem., 34: 2129-2137
(1994) for stannylation of chloro-containing thiophenes; and Lei et
al., Chem. Sci. DOI: 10.1039/c3sc50245g (2013) for chlorination of
bromo-containing aromatics.
Example 38
Preparation of additional
4,8-bis-substituted-2,6-bis-trimethylstannanyl-1,5-dithia-s-indacenes
##STR00084##
[0182] Various embodiments of repeating units (M.sup.1a) can be
prepared as follows. Briefly, an appropriate thieno-fused starting
compound can be reacted with n-butyl lithium in THF at room
temperature for about 1-1.5 hours before
1,5-dithia-s-indacene-4,8-dione is added. The mixture then can be
heated at about 50-60.degree. C. for 1-2 hours before cooling to
room temperature. This is followed by the addition of a solution of
SnCl.sub.2 in HCl/H.sub.2O, which is heated at about 50-60.degree.
C. for about 1-3 hours before cooling to room temperature. To
functionalize the repeating unit (M.sup.1a) with trimethylstannanyl
groups, n-butyl lithium again is added (room temperature, about 2
hours), before trimethyltin chloride is added in portions (room
temperature).
Example 39
Synthesis of Various Thieno-Fused Starting Compounds
Example 39A
Preparation of Naphthothiophene
##STR00085##
[0184] Both substituted and unsubstituted naphthothiophenes can be
prepared from an appropriate phthalic anhydride using the synthetic
route described in JP2010053094 (reproduced above), the entire
disclosure of which is incorporated by reference herein.
Example 39B
Preparation of Benzodithiophene
##STR00086## ##STR00087##
[0186] Substituted and unsubstituted benzodithiophenes can be
prepared via the synthetic routes provided above.
Example 39C
Preparation of Benzothienothiophene
##STR00088##
[0188] Various benzothienothiophenes can be prepared using the
synthetic route described above.
Example 39D
Preparation of Dithienothiophene
##STR00089##
[0190] Unsubstituted dithienothiophenes can be prepared via
synthetic route (a), (b) or (c) as described, respectively, in
Chem. Commun. 2002, 2424; J. Mater. Chem. 2003, 13, 1324; and Chem.
Commun. 2009, 1846, the entire disclosure of each of which is
incorporated by reference herein.
##STR00090##
[0191] Substituted dithienothiophenes can be prepared via synthetic
route (d), (e) or (f) as described, respectively, in J. Mater.
Chem. 2007, 17, 4972; Chem. Mater. 2007, 19, 4925; and Syn. Met.
1999, 987, the entire disclosure of each of which is incorporated
by reference herein.
Preparation of Thienothiophene
##STR00091##
[0193] Substituted thienothiophenes can be prepared using the
synthetic route described above.
Example 39F
Preparation of Benzothiophene
[0194] Substituted benzothiophenes can be prepared using the
synthetic routes described below.
##STR00092##
[0195] Device Fabrication
Example 40
Fabrication and Characterization of OPV Cells
[0196] Inverted OPVs were fabricated on ITO-covered glass that was
cleaned by sonication in soap water, water, acetone and isopropanol
followed by storage in a glass oven. Immediately before deposition
of the electron-injection layer, the substrates were UV ozone
treated for 20 minutes in a Jelight UVO Cleaner.RTM. 42. ZnO films
were prepared according to a previously published method. See Lloyd
et al., "Influence of the hole-transport layer on the initial
behavior and lifetime of inverted organic photovoltaics," Solar
Energy Materials and Solar Cells, 95,5, 1382-1388 (2011).
Donor:Acceptor (1:1 by weight) blend active layers were spin cast
from chloroform solutions. Some of the active layers were annealed
at temperatures ranging from about 80.degree. C. to about
180.degree. C. for about 3-10 minutes before deposition of the top
electrode. To complete the device fabrication, 8 nm of vanadium
oxide (V.sub.2O.sub.5) and 100 nm of aluminum were successively
deposited thermally under vacuum of .about.10.sup.-6 Torr. The
active area of the device was .about.0.09 cm.sup.2. The devices
were then encapsulated with a cover glass using EPO-TEK OG112-6 UV
curable epoxy (Epoxy Technology) in the glove box.
[0197] The photovoltaic characteristics of the encapsulated devices
were tested in air. The current density-voltage (J-V) curves were
obtained using a Keithley 2400 source-measure unit. The
photocurrent was measured under simulated AM1.5G irradiation (100
mW cm.sup.-2) using a xenon-lamp-based solar simulator (Newport
91160A 300 W Class-A Solar Simulator, 2 inch by 2 inch uniform
beam) with air mass 1.5 global filter. The light intensity was set
using an NREL calibrated silicon photodiode with a color
filter.
TABLE-US-00001 TABLE 1 JV characteristics of representative
donor:acceptor blend systems in inverted devices. All active layers
were processed from chloroform. Electron-Acceptor Electron-Donor
Polymer Polymer PCE (%) Ex. 3 Ex. 14 1.8 Ex. 3 Ex. 22 1.6 Ex. 3 Ex.
25 5.2 Ex. 9 Ex. 14 1.0 Ex. 9 Ex. 22 0.7 Ex. 9 Ex. 25 3.2 Ex. 3 Ex.
32 5.3 Ex. 9 Ex. 32 3.8 Ex. 3 Ex. 33 2.7 Ex. 8 Ex. 33 3.1
[0198] The present teachings encompass embodiments in other
specific forms without departing from the spirit or essential
characteristics thereof. The foregoing embodiments are therefore to
be considered in all respects illustrative rather than limiting on
the present teachings described herein. Scope of the present
invention is thus indicated by the appended claims rather than by
the foregoing description, and all changes that come within the
meaning and range of equivalency of the claims are intended to be
embraced therein.
* * * * *