U.S. patent application number 14/698040 was filed with the patent office on 2015-11-05 for visible/near-infrared porphyrin-tape/c60 organic photodetectors.
The applicant listed for this patent is The Regents of the University of Michigan, The University of Southern California. Invention is credited to Viacheslav Diev, Stephen R. Forrest, Kenneth Hanson, Mark E. Thompson, Jeramy D. Zimmerman.
Application Number | 20150318479 14/698040 |
Document ID | / |
Family ID | 42990178 |
Filed Date | 2015-11-05 |
United States Patent
Application |
20150318479 |
Kind Code |
A1 |
Forrest; Stephen R. ; et
al. |
November 5, 2015 |
Visible/Near-Infrared Porphyrin-Tape/C60 Organic Photodetectors
Abstract
Porphyrin compounds are provided. The compounds may further
comprise a fused polycyclic aromatic hydrocarbon or a fused
heterocyclic aromatic. Fused polycyclic aromatic hydrocarbon s and
fused heterocyclic aromatics may extend and broaden absorption, and
modify the solubility, crystallinity, and film-forming properties
of the porphyrin compounds. Additionally, devices comprising
porphyrin compounds are also provided. The porphyrin compounds may
be used in a donor/acceptor configuration with compounds, such as
C.sub.60.
Inventors: |
Forrest; Stephen R.; (Ann
Arbor, MI) ; Zimmerman; Jeramy D.; (Ann Arbor,
MI) ; Thompson; Mark E.; (Anaheim Hills, CA) ;
Diev; Viacheslav; (Los Angeles, CA) ; Hanson;
Kenneth; (Carrboro, NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Regents of the University of Michigan
The University of Southern California |
Ann Arbor
Los Angeles |
MI
CA |
US
US |
|
|
Family ID: |
42990178 |
Appl. No.: |
14/698040 |
Filed: |
April 28, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12868503 |
Aug 25, 2010 |
9017826 |
|
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14698040 |
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61341413 |
Mar 31, 2010 |
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61275156 |
Aug 26, 2009 |
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Current U.S.
Class: |
548/402 |
Current CPC
Class: |
C07F 7/2284 20130101;
H01L 51/0077 20130101; H01L 51/42 20130101; H01L 51/0058 20130101;
C07F 3/06 20130101; C09B 47/045 20130101; Y10S 428/917 20130101;
H01L 27/305 20130101; C07D 487/22 20130101; H01L 51/009 20130101;
C07F 7/24 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; H01L 51/42 20060101 H01L051/42; C07F 7/22 20060101
C07F007/22; C07F 3/06 20060101 C07F003/06; C07F 7/24 20060101
C07F007/24 |
Goverment Interests
GOVERNMENT SUPPORT
[0002] This invention was made with government support under
W15P7T-08-C-P409 awarded by Army/Cecom. The government has certain
rights in the invention.
Claims
1. A compound having the structure: ##STR00069## wherein R1-R24 are
independently selected from the group consisting of hydrogen,
hydroxyl, halogen, chalcogen, mercapto, alkyl, fluoroalkyl, alkoxy,
amino, cyano, alkenyl, alkynyl, aryl, and heteroaryl; wherein at
least two of R1-R24 are each a fused polycyclic aromatic group or a
fused heterocyclic aromatic group, wherein each fused polycyclic
aromatic group and fused heterocyclic aromatic group are fused to
the fused porphyrin of Formula I, wherein when the at least two
R1-R24 are adjacent, the at least two R1-R24 correspond to the same
fused polycyclic aromatic group or the fused heterocyclic aromatic
group; wherein M is a dicoordinate, tricoordinate, tetracoordinate,
pentacoordinate or hexacoordinate metal ion or 2 hydrogen atoms;
and wherein n is 0-100.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S. patent
application Ser. No. 12/868,503, filed Aug. 25, 2010, which
application claims benefit of U.S. Provisional Application Nos.
61/341,413, filed Mar. 31, 2010 and 61/275,156, filed Aug. 26,
2009, the contents of which are incorporated herein by reference in
their entireties.
JOINT RESEARCH AGREEMENT
[0003] The claimed invention was made by, on behalf of, and/or in
connection with one or more of the following parties to a joint
university corporation research agreement: Regents of the
University of Michigan, Princeton University, The University of
Southern California, and the Universal Display Corporation. The
agreement was in effect on and before the date the claimed
invention was made, and the claimed invention was made as a result
of activities undertaken within the scope of the agreement.
FIELD OF THE INVENTION
[0004] The present invention relates to novel organic compounds and
devices comprising these compounds. More specifically, the
invention relates to porphyrin oligomers and photodetectors
comprising porphyrin oligomer compounds in a donor/acceptor
configuration.
BACKGROUND
[0005] Opto-electronic devices that make use of organic materials
are becoming increasingly desirable for a number of reasons. Many
of the materials used to make such devices are relatively
inexpensive, so organic opto-electronic devices have the potential
for cost advantages over inorganic devices. In addition, the
inherent properties of organic materials, such as their
flexibility, may make them well suited for particular applications
such as fabrication on a flexible substrate. Examples of organic
opto-electronic devices include organic light emitting devices
(OLEDs), organic phototransistors, organic photovoltaic cells, and
organic photodetectors.
[0006] Photosensitive optoelectronic devices convert
electromagnetic radiation into electricity. Solar cells, also
called photovoltaic (PV) devices, are a type of photosensitive
optoelectronic device that is specifically used to generate
electrical power. Another type of photosensitive optoelectronic
device is a photoconductor cell. In this function, signal detection
circuitry monitors the resistance of the device to detect changes
due to the absorption of light. Another type of photosensitive
optoelectronic device is a photodetector. In operation a
photodetector is used in conjunction with a current detecting
circuit which measures the current generated when the photodetector
is exposed to electromagnetic radiation and may have an applied
bias voltage. A detecting circuit as described herein is capable of
providing a bias voltage to a photodetector and measuring the
electronic response of the photodetector to electromagnetic
radiation. Photosensitive devices may be used in a range of
devices, including photodetectors, imaging devices, photosensors,
and the like. Photosensitive devices and their fabrication and
operation are further described in U.S. Pat. Nos. 7,375,370 and
7,230,269, the disclosures of which are incorporated herein in
their entirety.
[0007] In addition to organic photosensitive and emissive devices,
organic materials may be used in various other electronic
components. For example, organic transistors may be constructed in
which some or all of the materials or structures in the transistor
include organic materials.
[0008] As used herein, the term "organic" includes polymeric
materials as well as small molecule organic materials that may be
used to fabricate organic opto-electronic devices. "Small molecule"
refers to any organic material that is not a polymer, and "small
molecules" may actually be quite large. Small molecules may include
repeat units in some circumstances. For example, using a long chain
alkyl group as a substituent does not remove a molecule from the
"small molecule" class. Small molecules may also be incorporated
into polymers, for example as a pendent group on a polymer backbone
or as a part of the backbone. Small molecules may also serve as the
core moiety of a dendrimer, which consists of a series of chemical
shells built on the core moiety.
[0009] As used herein, "top" means furthest away from the
substrate, while "bottom" means closest to the substrate. Where a
first layer is described as "disposed over" a second layer, the
first layer is disposed further away from substrate. There may be
other layers between the first and second layer, unless it is
specified that the first layer is "in contact with" the second
layer. For example, a cathode may be described as "disposed over"
an anode, even though there are various organic layers in
between.
[0010] As used herein, "solution processable" means capable of
being dissolved, dispersed, or transported in and/or deposited from
a liquid medium, either in solution or suspension form.
[0011] As used herein, and as would be generally understood by one
skilled in the art, a first "Highest Occupied Molecular Orbital"
(HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) energy level
is "greater than" or "higher than" a second HOMO or LUMO energy
level if the first energy level is closer to the vacuum energy
level. Since ionization potentials (IP) are measured as a negative
energy relative to a vacuum level, a higher HOMO energy level
corresponds to an IP having a smaller absolute value (an IP that is
less negative). Similarly, a higher LUMO energy level corresponds
to an electron affinity (EA) having a smaller absolute value (an EA
that is less negative). On a conventional energy level diagram,
with the vacuum level at the top, the LUMO energy level of a
material is higher than the HOMO energy level of the same material.
A "higher" HOMO or LUMO energy level appears closer to the top of
such a diagram than a "lower" HOMO or LUMO energy level.
[0012] In the context of organic materials, the terms "donor" and
"acceptor" refer to the relative positions of the HOMO and LUMO
energy levels of two contacting but different organic materials.
This is in contrast to the use of these terms in the inorganic
context, where "donor" and "acceptor" may refer to types of dopants
that may be used to create inorganic n- and p-types layers,
respectively. In the organic context, if the LUMO energy level of
one material in contact with another is lower, then that material
is an acceptor. Otherwise it is a donor. It is energetically
favorable, in the absence of an external bias, for electrons at a
donor-acceptor junction to move into the acceptor material, and for
holes to move into the donor material.
[0013] As used herein, and as would be generally understood by one
skilled in the art, a first work function is "greater than" or
"higher than" a second work function if the first work function has
a higher absolute value. Because work functions are generally
measured as negative numbers relative to vacuum level, this means
that a "higher" work function is more negative. On a conventional
energy level diagram, with the vacuum level at the top, a "higher"
work function is illustrated as further away from the vacuum level
in the downward direction. Thus, the definitions of HOMO and LUMO
energy levels follow a different convention than work
functions.
[0014] More details on organic devices, and the definitions
described above, can be found in U.S. Pat. No. 7,279,704, which is
incorporated herein by reference in its entirety.
SUMMARY OF THE INVENTION
[0015] Porphyrin compounds are provided, the compounds having the
structure:
##STR00001##
[0016] R.sub.1-R.sub.24 are independently selected from the group
consisting of hydrogen, hydroxyl, halogen, chalcogen, mercapto,
alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl, alkynyl, aryl,
and heteroaryl. One of R.sub.1-R.sub.24 is a fused polycyclic
aromatic or a fused heterocyclic aromatic. M is a dicoordinate,
tricoordinate, tetracoordinate, pentacoordinate or hexacoordinate
metal ion or 2 hydrogen atoms. n is 0-100. Preferably, n is
0-5.
[0017] In one aspect, M is selected from the group consisting of
Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Ho, Er, Tm, Yb, Lu, Th, U, Zn, ClAl, SnO, SnCl.sub.2, Pb(OAc), and
Sn(OH).sub.2. Preferably, M is Zn, Pb, Sn, ClAl, SnO, SnCl.sub.2,
Pb(OAc), and Sn(OH).sub.2.
[0018] In one aspect, one of R.sub.1-R.sub.24 is a fused pyrene.
Preferably, one of R.sub.1-R.sub.9 and R.sub.13-R.sub.21 is a fused
pyrene.
[0019] In one aspect, the compound is selected from the group
consisting of:
##STR00002## ##STR00003## ##STR00004## ##STR00005## ##STR00006##
##STR00007## ##STR00008##
[0020] R.sub.1-R.sub.63 are independently selected from the group
consisting of hydrogen, alkyl, fluoroalkyl, alkoxy, amino, cyano,
alkenyl, alkynyl, aryl, and heteroaryl. Each dotted arc is a
polycyclic aromatic substituent or a heterocyclic aromatic
substituent. X may be dicoordinate, tricoordinate, tetracoordinate,
or hexacoordinate. X is selected from the group consisting of O, S,
Se, Te, N, P, As, Si, Ge, and B.
[0021] The dotted arc is a substituent that forms a closed ring,
which may extend the conjugation of the pi-system. In one aspect,
the substituent is selected from the group consisting of:
##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013##
##STR00014## ##STR00015##
[0022] i, j, and m are each independently 0-100. The zig zag line
represents the fusion points of the pi-extended unit to the
porphyrin. The dot represents the point where the substituent is
connected to the meso position of the porphryin. X is O, S, Se, Te,
N, P, As, Si, Ge, or B. Y is H, M, or X. R'.sub.1-R'.sub.23 are
independently selected from hydrogen, hydroxyl, halogen, chalcogen,
mercapto, alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl,
alkynyl, aryl, and heteroaryl.
[0023] Preferably, the dotted arc substituent is naphthalene,
anthracene, or pyrene.
[0024] Specific examples of the porphyrin compounds are provided.
In one aspect, the compound is selected from the group consisting
of:
##STR00016## ##STR00017## ##STR00018##
[0025] An organic device is also provided. The device comprises a
first electrode, a second electrode, a first layer, disposed
between the first electrode and the second electrode, and a second
layer comprising a second organic compound disposed between the
first electrode and the second electrode, wherein the second layer
is in direct contact with the first layer.
[0026] The first layer comprises a first compound, wherein the
first compound has the structure of Formula I, as described
above.
[0027] R.sub.1-R.sub.24 are independently selected from the group
consisting of hydrogen, hydroxyl, halogen, chalcogen, mercapto,
alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl, alkynyl, aryl,
and heteroaryl. M is a dicoordinate, tricoordinate,
tetracoordinate, pentacoordinate or hexacoordinate metal ion or 2
hydrogen atoms. n is 0-100. Preferably, n is 0-5.
[0028] In one aspect, at least one of R.sub.1-R.sub.24 is a fused
polycyclic aromatic or a fused heterocyclic aromatic. Preferably,
at least one of R.sub.1-R.sub.24 is a fused pyrene. More
preferably, at least one of R.sub.1-R.sub.9 and R.sub.13-R.sub.21
is a fused pyrene.
[0029] In another aspect, the first layer is in contact with the
first electrode and the device further comprises a layer of BCP
disposed between and in contact with the second layer and the
second electrode.
[0030] In one aspect, M is selected from the group consisting of
Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Ho, Er, Tm, Yb, Lu, Th, U, Zn, ClAl, SnO, SnCl.sub.2, Pb(OAc), and
Sn(OH).sub.2. Preferably, M is Zn, Pb, Sn, ClAl, SnO, SnCl.sub.2,
Pb(OAc), and Sn(OH).sub.2.
[0031] In one aspect, the second compound is selected from the
group consisting of C.sub.60, C.sub.70, C.sub.84, F.sub.16--CuPc,
PTCBI, PTCDA, PCBM or PTCDI. Preferably, the second compound is
C.sub.60.
[0032] In one aspect, the device has an optical response at a
wavelength greater than 1200 nm. In another aspect, the device has
an optical response at a wavelength greater than 1500 nm.
[0033] In one aspect, the first layer is disposed using solution
processing.
[0034] In another aspect, the first layer comprises more than one
first compound.
[0035] In yet another aspect, the second compound is disposed in a
layer having a thickness of about 80 nm to about 200 nm.
[0036] In one aspect, the first compound is disposed in combination
with one or more of polystyrene, chlorobenzene, toluene, methylene
chloride, dichloromethane, chloroform, chloronaphthalene,
dichlorobenzene, and pyridine.
[0037] Specific example of devices comprising porphyrin compounds
are provided. In one aspect, the first compound is selected from
the group consisting of Formula II-Formula XVIII.
[0038] R.sub.1-R.sub.63 are independently selected from the group
consisting of hydrogen, alkyl, fluoroalkyl, alkoxy, amino, cyano,
alkenyl, alkynyl, aryl, and heteroaryl. Each dotted arc is a
polycyclic aromatic substituent or a heterocyclic aromatic
substituent. X may be dicoordinate, tricoordinate, tetracoordinate,
or hexacoordinate. X is selected from the group consisting of O, S,
Se, Te, N, P, As, Si, Ge, and B.
[0039] The dotted arc is a substituent that forms a closed ring
that may extend the conjugation of the pi-system. In one aspect,
the substituent is selected from the group consisting of:
##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023##
##STR00024## ##STR00025##
[0040] i, j, and m are each independently 0-100. The zig zag line
represents the fusion points of the pi-extended unit to the
porphyrin. The dot represents the point where the substituent is
connected to the meso position of the porphryin. X is O, S, Se, Te,
N, P, As, Si, Ge, or B. Y is H, M, or X. R'.sub.1-R'.sub.23 are
independently selected from hydrogen, hydroxyl, halogen, chalcogen,
mercapto, alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl,
alkynyl, aryl, and heteroaryl.
[0041] Preferably, the dotted arc is naphthalene, anthracene, or
pyrene.
[0042] In another aspect, the first compound is selected from the
group consisting of Compound 1-Compound 11.
[0043] In yet another aspect, the device is a consumer product.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] FIG. 1 shows monomer, dimer and trimer absorption features,
showing how response wavelength can be increased by using longer
oligomers.
[0045] FIG. 2 shows the effect of fusing anthracene is shown. A
two-sided fused molecule extends and broadens conjugation more than
the one-sided fused molecule
[0046] FIG. 3 shows four Zn-dimers with different end and side
substituted variants. This chart is referenced in later charts.
[0047] FIG. 4 shows film absorbance of A, C, and D (see FIG. 3).
Various changes to the end substitutions has little effect on
absorption wavelength.
[0048] FIG. 5 shows typical I-V and EQE data for "A", "B", "C", and
"D" (see FIG. 3). Devices with "A", "B" and "C" have a 1:10
polystyrene:dimer ratio to help with film forming and increase
device yield. All devices are cast on ITO/PEDOT and have
.about.1000 .ANG. of C.sub.60, 100 .ANG. BCP, and 1000 .ANG.
Ag.
[0049] FIG. 6 shows typical illuminated IV, EQE, and specific
detectivity (D*) for molecule "C".
[0050] FIG. 7 shows film absorbance (left) of pyrene substituted
and pyrene fused dimers. Substituted dimer is shown at top right,
and the fused dimer is shown at bottom right.
[0051] FIG. 8 shows illuminated IV, EQE, and D* data for pyrene
substituted dimer with 1000 .ANG. C.sub.60 (film is approximately
the same thickness as shown in FIG. 7.). Film was cast from
chlorobenzene.
[0052] FIG. 9 shows illuminated IV, EQE, and D* data for pyrene
fused dimer with 1250 .ANG. C.sub.60 (film is the same thickness as
shown in FIG. 7.) Film was cast from 99% chlorobenzene+1%
pyridine.
[0053] FIG. 10 shows the effect of different core metallizations is
shown. SnCl.sub.2 and Pb both extend the wavelength response;
[0054] FIG. 11 Absorption spectra of anthracene fused porphyrin
dimers.
[0055] FIG. 12 shows the scheme for the synthesis of pyrene zinc
porphyrin dimer and subsequent fusion of pyrene rings with
porphyrin tape.
[0056] FIG. 13 shows the pronounced effect of aggregation in
solution for fused product in comparison to starting porphyrin
dimer is shown. .sup.1H-NMR spectra for pyrene porphyrin dimer and
porphyrin dimer with fused pyrene rings are shown in 5%
pyridine-d.sub.5/CDCl.sub.3 (top) and in 5%
pyridine-d.sub.5/C.sub.6D.sub.6 (fused pyrene dimer, bottom).
[0057] FIG. 14 shows the scheme for the synthesis of fused
anthracene zinc porphyrin dimers.
[0058] FIG. 15 shows absorption coefficients (a) of the four
molecules studied: DTBPh, solid line, (circles); CNPh, long-dashed
line (squares); Psub, short-dashed line (triangles); and Pfused,
dotted line (diamonds). Inset: Chemical structures of molecules
studied. All donors use the same porphyrin-dimer base, and differ
only in their end terminations. For CNPh, R.dbd.R1, X.dbd.H; DTBPh,
R.dbd.R2, X.dbd.H; Psub, R.dbd.R3, X.dbd.H; and Pfused, R.dbd.R4
where X', is the second bond to the pyrene.
[0059] FIG. 16 shows atomic force micrographs of films deposited by
doctor blading a 0.5 wt/vol % solution in chlorobenzene of (a)
CNPh, (b) CNPh with 1 vol % pyridine, (c) DTBPh, (d) Psub, and (e)
Pfused with 1% pyridine. The vertical scale range of the respective
micrographs are 110 nm, 80 nm, 20 nm 20 nm, and 40 nm. The RMS
roughnesses of the films are 20 nm, 9.0 nm 0.5 nm, 2.7 nm, and 5.3
nm, respectively.
[0060] FIG. 17 (a) shows X-ray diffraction intensity of films
consisting of the various porphyrin tape molecules indicated. (b)
shows the orientation if the molecules with respect to the
substrate surface (black horizontal line). The (001) plane is
parallel to the substrate surface, the projection of the (100)
plane is shown by the parallelogram, and projections of the b- and
c-directions of the unit cell are labeled. c* denotes the direction
perpendicular to the (001) plane and lies within the plane of the
paper.
[0061] FIG. 18 shows current density vs. voltage characteristics of
the porphyrin tape/C.sub.60 photodetectors. Ideality factors and
specific series resistances for detectors based on the several
materials studied are DTBPh: n=1.31.+-.0.11 and Rs=530.+-.160
.OMEGA.-cm, CNPh: n=1.81.+-.0.04 and Rs=5.8.+-.2.1 .OMEGA.-cm,
Psub: n=1.35.+-.0.02 and Rs=0.90.+-.0.1 .OMEGA.-cm, and Pfused:
n=1.33.+-.0.03 and Rs=1.4.+-.0.1 .OMEGA.-cm.
[0062] FIG. 19 shows external quantum efficiencies of devices
fabricated from the several porphyrin-tape compounds are shown with
the heavy lines (upper set). Specific detectivity of the same
devices are shown in the lighter lines (lower set). Line types are:
DTBPh, solid; CNPh, dot-dash; Psub, dashed; and Pfused, dotted.
[0063] FIG. 20 shows the electrical response of a 0.3 mm diameter
device biased at -1 V using a 1 ns pulse at .lamda.=1064 nm. The
fit corresponds to a decay time constant of 1.87.+-.0.03 ns. Inset:
Bode plot of the electrical response, indicating a 3 dB roll-off
frequency of 56.+-.7 MHz.
[0064] FIG. 21 illustrates absorption of spectra of fused
anthracene-porphoryin dimer VI.
DETAILED DESCRIPTION
[0065] Porphyrin oligomers are provided herein, which may be used
in a donor/acceptor configuration as a photodetector or
photovoltaic material. Specifically, porphyrin tapes comprising
fused polyaromatic hydrocarbons (PAHs) and fused heterocyclic
aromatics are provided. Fused PAHs and fused heterocyclic aromatics
may extend and broaden absorption, and modify the solubility,
crystallinity, and film-forming properties of the porphyrin
compounds.
[0066] Historically, organic photodetectors have been limited to
wavelengths less than .about.1000 nm. Difficulties in creating
organic photodetectors can be traced to difficulties extending
conjugation into larger molecules while maintaining sufficient
exciton lifetime so that excitons have sufficient time to diffuse
to a donor/acceptor interface where exciton dissociation can occur.
Materials with infrared absorption will have a narrower HOMO/LUMO
energy gap than those that absorb in the visible making pairing
with an appropriate donor or acceptor more difficult.
[0067] Porphyrin molecules are well known visible absorbers.
Oligomers of porphyrins can be made by fusing two porphyrins
together with three carbon-carbon bonds between porphyrins (FIG.
1), extending conjugation and thus absorption out to 1200 nm for a
dimer, or 1500 nm for the trimer. A second method of extending
conjugation is to fuse a polycyclic aromatic hydrocarbon (PAH),
such as pyrene or anthracene to the ends of the porphyrin as seen
in FIG. 2. This extends conjugation, increases the absorption
wavelength, and broadens the absorption into wider bands. A third
way of extending absorption is by modifying the core of the
porphyrin. The core may contain two hydrogen atoms, a metal atom
with valence of 2+ (i.e. Zn, Pb, Sn(II), etc), or a metal complex
with an overall valence of 2+ (i.e. ClAl, Sn(IV)O, Sn(IV)Cl.sub.2,
etc), the metal can change the absorption energy and intensity.
Also, different end structures and core metals will change the
solubility in various solvents, propensity to crystallize,
film-forming properties, and transport properties such as carrier
mobility and exciton diffusion length.
[0068] The energetics of the porphyrin oligomers are similar to
single porphyrins but with a narrower band gap and demonstrating
shorter excited state lifetimes; however, we have shown traditional
acceptors such as C.sub.60, may be utilized. Different end and side
groups (e.g. methoxy or cyano groups) will raise or lower the
energetics, which may be used to change open circuit voltage and
dark current in a detector.
[0069] Porphyrins are one of the most important biological
molecules essential for life and responsible in nature for such
oxidation-reduction reactions as photosynthesis in plants and
respiration in animals. (Wasielewski, M. R., Chem. Rev. 1992,
435-461, and references therein; Harriman, A., Sauvage, J.-P.,
Chem. Soc. Rev. 1996, 24, 41-48, and references therein; Murakami,
Y., Kikuchi, J.-i., Hisaeda, Y., Hayashida, O., Chem. Rev. 1996,
96, 721-758, and references therein). Synthetic porphyrins have
broad applications as useful opto-electronic materials in different
fields of organoelectronics (Applications: Past, Present and
Future. The Porphyrin Handbook; Kadish, K. M., Smith, K. M. and
Guilard, R., Eds.; Academic Press: San Diego, Calif., 2000; Vol. 6;
Electron Transfer. The Porphyrin Handbook; Kadish, K. M., Smith, K.
M. and Guilard, R., Eds.; Academic Press: San Diego, Calif., 2000;
Vol. 8. Some most recent examples; Perez, M. D., Borek, C.,
Djurovich, P. I., Mayo, E. I., Lunt, R. R., Forrest, S. R.,
Thompson, M. E., Adv. Mater. 2009, 21, 1517-1520; Imahori, H.,
Umeyama, T., Ito, S., Acc. Chem. Res. 2009, ACS ASAP,
10.1021/ar900034t; Liu, Y., Feng, X., Shen, P., Zhou, W., Weng, C.,
Zhao, B., Tan, S., Chem. Comm. 2009, 2499-2501; and Che, C.-M.,
Chui, S. S.-Y., Xu, Z.-X., Roy, V. A. L., Yan. J. J., Fu, W.-F.,
Lai, P. T., Williams, I. D., Che. Asia. J. 2008, 3, 1092-1103),
such as solar cells, photodetectors, as catalysts in a variety of
reaction (Biochemistry and Binding: Activation of Small Molecules.
The Porphyrin Handbook; Kadish, K. M., Smith, K. M. and Guilard,
R., Eds.; Academic Press: San Diego, Calif., 2000; Vol. 4; Lu, Y.,
Yeung, N., Sieracki, N., Marshall, N. M., Nature, 2009, 855-862.
(b) Doyle, M. P., Angew. Chem. Int. Ed. 2009, 48, 850-852; Thu,
H-Y., Tong, G. S-M., Huang, J-S., Chan, S. L-F., Deng, Q-H., Che,
C-M., Angew. Chem. Int. Ed. 2008, 47, 9747-9751), bioimaging agents
and biologically active ingredients in medicine (Medical Aspects of
Porphyrins. The Porphyrin Handbook; Kadish, K. M., Smith, K. M. and
Guilard, R., Eds.; Academic Press: San Diego, Calif., 2003; Vol.
14). Advantages of usage of porphyrins as opto-electronic materials
include efficiency of charge separation and charge transport even
in thick films of assembled porphyrins (Huijser, A., Savenije, T.
J., Meskers, S. C. J., Vermeulen, M. J., Siebbeles, L. D. A., J.
Am. Chem. Soc. 2008, 130, 12496-12500; Winters, M. U., Dahlstedt,
E. D., Blades, H. E., Wilson, C. J., Frampton, M. J., Anderson, H.
L., Albinsson, B, J. Am. Chem. Soc. 2007, 129, 4291-4297;
Siebbeles, L. D. A., Huijser, A., Savenije, T. J., J. Mater. Chem.
2009, 19, 6067-6072; Huijser, A., Suijkerbuijk, B. M. J. M., Klein
Gebbink, R, J. M., Savenije, T. J., Siebbeles, L. D. A., J. Am.
Chem. Soc. 2008, 130, 2485-2492), strong absorbance in the visible
region, high chemical stability, ability to tune optoelectronic
properties (Applications: Past, Present and Future. The Porphyrin
Handbook; Kadish, K. M., Smith, K. M. and Guilard, R., Eds.;
Academic Press: San Diego, Calif., 2000; Vol. 6; Electron Transfer.
The Porphyrin Handbook; Kadish, K. M., Smith, K. M. and Guilard,
R., Eds.; Academic Press: San Diego, Calif., 2000; Vol. 8; Perez,
M. D., Borek, C., Djurovich, P. I., Mayo, E. I., Lunt, R. R.,
Forrest, S. R., Thompson, M. E., Adv. Mater. 2009, 21, 1517-1520;
Imahori, H., Umeyama, T., Ito, S., Acc. Chem. Res. 2009, ACS ASAP,
10.1021/ar900034t; Liu, Y., Feng, X., Shen, P., Zhou, W., Weng, C.,
Zhao, B., Tan, S., Chem. Comm. 2009, 2499-2501; and Che, C.-M.,
Chui, S. S.-Y., Xu, Z.-X., Roy, V. A. L., Yan. J. J., Fu, W.-F.,
Lai, P. T., Williams, I. D., Che. Asia. J. 2008, 3, 1092-1103).
Considerable attention has been paid recently to multi-porphyrin
systems composed of porphyrin arrays (Beletskaya, I., Tyurin, V.
S., Tsivadze, A. Yu., Guilard, R., Stern, C., Chem. Rev. 2009, 109,
1659-1713; Fukuzumi, S., Kojima, T., J. Mater. Chem. 2008, 18,
1427-1439). Oligomers of porphyrins made by fusing porphyrins
together with three carbon-carbon bonds between porphyrin units
(porphyrin tapes) represent highly conjugated systems with extended
absorption into Near IR region (for example, 1200 nm for a dimer of
zinc porphyrin, or 1500 nm for the trimer of zinc porphyrin)
(Tsuda, A., Osuka, A., Science, 2001, 293, 79-82; Tsuda, A.,
Furuta, H., Osuka, A., J. Am. Chem. Soc. 2001, 123, 10304-10321;
Cho, H. S., Jeong, D. H., Cho, S., Kim, D., Matsuzaki, Y., Tanaka,
K., Tsuda, A., Osuka, A., J. Am. Chem. Soc. 2002, 124, 14642-14654;
and Tsuda, A., Bull. Chem. Soc, Jpn., 2009, 82, 11-28).
[0070] A second way of extending absorption is by modifying the
core of the porphyrin. The core may contain two hydrogen atoms, or
a metal atom with valence of 2+ (i.e. Zn, Pb, Sn(II), etc), or a
metal complex with an overall valence of 2+ (i.e. ClAl, Sn(IV)O,
Sn(IV)Cl.sub.2, etc), the metal changes the absorption energy and
intensity. A new method of extending conjugation is to fuse a
polycyclic aromatic hydrocarbon (PAH), such as pyrene or anthracene
to the ends of the porphyrin as shown previously to occur with the
formation of mono-fused porphyrins (Yamane, O., Sugiura, K-i.,
Miyasaka, H., Nakamura, K., Fujumoto, T., Nakamura, K., Kaneda, T.,
Sakata, Y., Yamashita, M., Chem. Lett. 2004, 33, 40-42; Tanaka, M.,
Hayashi, S., Eu, S., Umeyama, T., Matano, Y., Imahori, H., Chem.
Comm. 2007, 2069-2071; and Davis, N. K. S., Pawlicki, M., Anderson,
H. L., Org. Lett. 2008, 10, 3945-3947). This extends conjugation,
increases the absorption wavelength and broadens the absorption
into wider bands together with an increased intensity of the Q
bands relative to that of the Soret band. However fusion of PAHs
with porphyrins requires the presence of activating groups, such as
methoxy or carboxy groups and does not occur with unsubstituted
PAHs (Yamane, O., Sugiura, K-i., Miyasaka, H., Nakamura, K.,
Fujumoto, T., Nakamura, K., Kaneda, T., Sakata, Y., Yamashita, M.,
Chem. Lett. 2004, 33, 40-42; Tanaka, M., Hayashi, S., Eu, S.,
Umeyama, T., Matano, Y., Imahori, H., Chem. Comm. 2007, 2069-2071;
and Davis, N. K. S., Pawlicki, M., Anderson, H. L., Org. Lett.
2008, 10, 3945-3947). Also to the best of our knowledge fusion was
not shown to proceed with more than one aromatic ring to form
end-capped porphyrins. On the other hand, porphyrin tapes have
different oxidation-reduction properties and have narrower energy
gaps (Cho, H. S., Jeong, D. H., Cho, S., Kim, D., Matsuzaki, Y.,
Tanaka, K., Tsuda, A., Osuka, A., J. Am. Chem. Soc. 2002, 124,
14642-14654). This could facilitate fusion reaction with PAHs as
well as multiple fusion reactions could be possible within one
porphyrin molecule without need to use activation groups. Herein,
absorption and synthesis of a new class of hybrids of porphyrin
tapes and PAHs composed by connecting both termini of tapes and
PAHs with two or three carbon-carbon bonds are provided.
[0071] Unless otherwise specified, any of the layers of the various
embodiments may be deposited by any suitable method. For the
organic layers, preferred methods include thermal evaporation,
ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and
6,087,196, which are incorporated by reference in their entireties,
organic vapor phase deposition (OVPD), such as described in U.S.
Pat. No. 6,337,102 to Forrest et al., which is incorporated by
reference in its entirety, and deposition by organic vapor jet
printing (OVJP), such as described in U.S. patent application Ser.
No. 10/233,470, which is incorporated by reference in its entirety.
Other suitable deposition methods include spin coating and other
solution based processes. Solution based processes are preferably
carried out in nitrogen or an inert atmosphere. For the other
layers, preferred methods include thermal evaporation. Preferred
patterning methods include deposition through a mask, cold welding
such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which
are incorporated by reference in their entireties, and patterning
associated with some of the deposition methods such as ink-jet and
OVJD. Other methods may also be used. The materials to be deposited
may be modified to make them compatible with a particular
deposition method. For example, substituents such as alkyl and aryl
groups, branched or unbranched, and preferably containing at least
3 carbons, may be used in small molecules to enhance their ability
to undergo solution processing. Substituents having 20 carbons or
more may be used, and 3-20 carbons is a preferred range. Materials
with asymmetric structures may have better solution processability
than those having symmetric structures, because asymmetric
materials may have a lower tendency to recrystallize. Dendrimer
substituents may be used to enhance the ability of small molecules
to undergo solution processing.
[0072] Devices fabricated in accordance with embodiments of the
invention may be incorporated into a wide variety of consumer
products, including flat panel displays, computer monitors,
televisions, billboards, lights for interior or exterior
illumination and/or signaling, heads up displays, fully transparent
displays, flexible displays, laser printers, telephones, cell
phones, personal digital assistants (PDAs), laptop computers,
digital cameras, camcorders, viewfinders, micro-displays, vehicles,
a large area wall, theater or stadium screen, or a sign. Various
control mechanisms may be used to control devices fabricated in
accordance with the present invention, including passive matrix and
active matrix. Many of the devices are intended for use in a
temperature range comfortable to humans, such as 18 degrees C. to
30 degrees C., and more preferably at room temperature (20-25
degrees C.).
[0073] The materials and structures described herein may have
applications in many organic devices. For example, other
optoelectronic devices such as OLEDs, organic solar cells and
organic photodetectors may employ the materials and structures.
More generally, organic devices, such as organic transistors, may
employ the materials and structures.
[0074] The terms halo, halogen, alkyl, cycloalkyl, alkenyl,
alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and
heteroaryl are known to the art, and are defined in U.S. Pat. No.
7,279,704 at cols. 31-32, which are incorporated herein by
reference.
[0075] Porphyrin oligomers and devices containing these compounds
are provided. The porphyrin compounds are in a donor/acceptor
configuration typical with more common small molecule organic
photodetectors operating at visible wavelengths (i.e. copper
phthalocyanine/C.sub.60). The porphyrin oligomer may act as a donor
and paired with an acceptor, such as C.sub.60. One implementation
is to deposit the detectors in a bottom illumination configuration.
A glass substrate is used with a transparent conducting layer such
as indium tin oxide (ITO), followed by a optional layer of
PEDOT:PSS to aid in forming subsequent layers, followed by solution
deposition of a soluble porphyrin or thermal evaporation of a
sublimable porphyrin, thermal evaporation of an acceptor such as
C.sub.60 of thickness.apprxeq.80-200 nm, and finally, evaporation
of contacts such as BCP/silver or LiF/aluminum.
[0076] Porphyrin compounds are provided, the compounds having the
structure:
##STR00026##
[0077] R.sub.1-R.sub.24 are independently selected from the group
consisting of hydrogen, hydroxyl, halogen, chalcogen, mercapto,
alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl, alkynyl, aryl,
and heteroaryl. One of R.sub.1-R.sub.24 is a fused polycyclic
aromatic or a fused heterocyclic aromatic. M is a dicoordinate,
tricoordinate, tetracoordinate, pentacoordinate or hexacoordinate
metal ion or 2 hydrogen atoms. n is 0-100. Preferably, n is 0-5.
When n is 5, the compounds exhibits a wavelength response at about
2500 nm. Without being bound by theory, it is believed that the
excited state is localized on a relatively small section of the
compound. Therefore, extending the porphoryin oligomer beyond five
units may not change the wavelength response of the compound.
[0078] In one aspect, M is selected from the group consisting of
Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Ho, Er, Tm, Yb, Lu, Th, U, Zn, ClAl, SnO, SnCl.sub.2, Pb(OAc), and
Sn(OH).sub.2. Preferably, M is Zn, Pb, Sn, ClAl, SnO, SnCl.sub.2,
Pb(OAc), and Sn(OH).sub.2.
[0079] In one aspect, one of R.sub.1-R.sub.24 is a fused pyrene.
Preferably, one of R.sub.1-R.sub.9 and R.sub.13-R.sub.21 is a fused
pyrene.
[0080] In one aspect, the compound is selected from the group
consisting of:
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032##
[0081] R.sub.1-R.sub.63 are independently selected from the group
consisting of hydrogen, alkyl, fluoroalkyl, alkoxy, amino, cyano,
alkenyl, alkynyl, aryl, and heteroaryl. Each dotted arc is a
polycyclic aromatic substituent or a heterocyclic aromatic
substituent. X may be dicoordinate, tricoordinate, tetracoordinate,
or hexacoordinate. X is selected from the group consisting of O, S,
Se, Te, N, P, As, Si, Ge, and B.
[0082] The dotted arc is a substituent that forms a closed ring,
which may extend the conjugation of the pi-system. For example, the
structure
##STR00033##
may be described as
##STR00034##
[0083] In another aspect, the dotted arc is a substituent selected
from the group consisting of:
##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039##
##STR00040## ##STR00041##
[0084] i, j, and m are each independently 0-100. The zig zag line
represents the fusion points of the pi-extended unit to the
porphyrin. The dot represents the point where the substituent is
connected to the meso position of the porphryin. X is O, S, Se, Te,
N, P, As, Si, Ge, or B. Y is H, M, or X. R'.sub.1-R'.sub.23 are
independently selected from hydrogen, hydroxyl, halogen, chalcogen,
mercapto, alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl,
alkynyl, aryl, and heteroaryl.
[0085] In the group of substituents provided above, the porphyrin
tape is not shown explicitly. The "dot" in these images represents
the point where the substituent is connected to the meso position
of the porphryin. The "zig-zag" line delineates the fusion points
of the pi-extended unit to the porphyrin. The following
illustration is a non-limiting example depicting the "dot"
indicating the positions of fusion of a polycyclic aromatic group
fused to a porphyrin and the "zig zag" line indicating positions of
connection with the meso position of the porphyrin ring.
##STR00042##
[0086] Preferably, the dotted arc substituent is naphthalene,
anthracene, or pyrene. Most preferably, the dotted arc is pyrene.
Without being bound by theory, it is believed that fused pyrene
results in twisting, which increases the solubility of the
compound, this improving processability. Compounds with improved
solubility may be particularly beneficial to make thin films.
[0087] Specific examples of the porphyrin compounds are provided.
In one aspect, the compound is selected from the group consisting
of:
##STR00043## ##STR00044## ##STR00045## ##STR00046##
[0088] An organic device is also provided. The device comprises a
first electrode, a second electrode, a first layer, disposed
between the first electrode and the second electrode, and a second
layer comprising a second organic compound disposed between the
first electrode and the second electrode, wherein the second layer
is in direct contact with the first layer.
[0089] The first layer comprises a first compound, wherein the
first compound has the structure:
##STR00047##
[0090] R.sub.1-R.sub.24 are independently selected from the group
consisting of hydrogen, hydroxyl, halogen, chalcogen, mercapto,
alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl, alkynyl, aryl,
and heteroaryl. M is a dicoordinate, tricoordinate,
tetracoordinate, pentacoordinate or hexacoordinate metal ion or
alternatively 2 hydrogen atoms. n is 0-100. Preferably, n is
0-5.
[0091] In one aspect, at least one of R.sub.1-R.sub.24 is a fused
polycyclic aromatic or a fused heterocyclic aromatic. Preferably,
at least one of R.sub.1-R.sub.24 is a fused pyrene. More
preferably, at least one of R.sub.1-R.sub.9 and R.sub.13-R.sub.21
is a fused pyrene.
[0092] In another aspect, the first layer is in contact with the
first electrode and the device further comprises a layer of BCP
disposed between and in contact with the second layer and the
second electrode.
[0093] In one aspect, M is selected from the group consisting of
Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Ho, Er, Tm, Yb, Lu, Th, U, Zn, ClAl, SnO, SnCl.sub.2, Pb(OAc), and
Sn(OH).sub.2. Preferably, M is Zn, Pb, Sn, ClAl, SnO, SnCl.sub.2,
Pb(OAc), and Sn(OH).sub.2.
[0094] In one aspect, the second compound is selected from the
group consisting of C.sub.60, C.sub.70, C.sub.84, F.sub.16--CuPc,
PTCBI, PTCDA, PCBM or PTCDI. Preferably, the second compound is
C.sub.60.
[0095] In one aspect, the device has an optical response at a
wavelength greater than 1200 nm. In another aspect, the device has
an optical response at a wavelength greater than 1500 nm.
[0096] In one aspect, the first layer is disposed using solution
processing.
[0097] In another aspect, the first layer comprises more than one
first compound.
[0098] In yet another, the second compound is disposed in a layer
having a thickness of about 80 nm to about 200 nm.
[0099] In one aspect, the first compound is disposed in combination
with one or more of polystyrene, chlorobenzene, toluene, methylene
chloride, dichloromethane, chloroform, chloronaphthalene,
dichlorobenzene, and pyridine.
[0100] Specific example of devices comprising porphyrin compounds
are provided. In one aspect, the first compound is selected from
the group consisting of:
##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052##
##STR00053##
[0101] R.sub.1-R.sub.63 are independently selected from the group
consisting of hydrogen, alkyl, fluoroalkyl, alkoxy, amino, cyano,
alkenyl, alkynyl, aryl, and heteroaryl. Each dotted arc is a
polycyclic aromatic substituent or a heterocyclic aromatic
substituent. X may be dicoordinate, tricoordinate, tetracoordinate,
or hexacoordinate. X is selected from the group consisting of O, S,
Se, Te, N, P, As, Si, Ge, and B.
[0102] The dotted arc is a substituent that forms a closed ring. As
discussed above, the substituent may extend the conjugation of the
pi-system. In one aspect, the dotted arc is a substituent selected
from the group consisting of:
##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##
##STR00059## ##STR00060##
[0103] i, j, and m are each independently 0-100. The zig zag line
represents the fusion points of the pi-extended unit to the
porphyrin. The dot represents the point where the substituent is
connected to the meso position of the porphryin. X is O, S, Se, Te,
N, P, As, Si, Ge, or B. Y is H, M, or X. R'.sub.1-R'.sub.23 are
independently selected from hydrogen, hydroxyl, halogen, chalcogen,
mercapto, alkyl, fluoroalkyl, alkoxy, amino, cyano, alkenyl,
alkynyl, aryl, and heteroaryl. As discussed above, the porphryin
tape is not shown explicitly in the above listing of substituents.
The "dot" in these images represents the point where the polycyclic
aromatic group is connected to the meso position of the porphryin.
The "zig-zag" line delineates the fusion points of the pi-extended
unit to the porphyrin.
[0104] Preferably, the dotted arc substituent is naphthalene,
anthracene, or pyrene.
[0105] In another aspect, the first compound is selected from the
group consisting of:
##STR00061## ##STR00062## ##STR00063## ##STR00064##
[0106] In yet another aspect, the device is a consumer product.
EXPERIMENTAL
Compound Examples
Example 1
Fusion of Pyrene Rings with Zinc Porphyrin Dimer. (See FIG. 12)
4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane
[0107] To a ca. 0.1 M solution of 1-bromopyrene in toluene 10 mol %
of Cl.sub.2Pd(PPh.sub.3).sub.2, 5 equivalents of picolineborane and
10 equivalents of triethylamine was added. Reaction mixture was
degassed with nitrogen and refluxed overnight. Reaction mixture was
quenched with water, toluene was distilled off and the residue was
subjected to column chromatography on silica gel (gradient eluation
with hexanes-ethyl acetate mixtures from 1:0 to 1000:5) to give
70-80% of 4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane.
.sup.1H-NMR (CDCl.sub.3, 400 MHz): 1.51 (s, 12H), 8.02 (t, 1H,
J=7.7 Hz), 8.07-8.24 (m, 6H), 8.56 (d, 1H, J=9.7 Hz), 9.09 (d, 1H,
J=9.7 Hz). MALDI TOF: 328 (M.sup.+), requires 328.16 for
C.sub.22H.sub.21BO.sub.2.
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)porphyrinato(2-)-.kappa.N-
.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)zinc(II)
(see FIG. 12)
[0108] A) NBS (1.54 g, 8.7 mmol, 1.3 equiv.) was added to a stirred
solution of porphyrin I (FIG. 12, compound I, 5 g, 6.7 mmol) in
dichloromethane (300 mL) and pyridine (5 ml) at -10.degree. C.
(NaCl/ice bath) under nitrogen atmosphere. Reaction mixture was
stirred at the same temperature for 10 min the was allowed to warm
to 0.degree. C. in 5 min (water bath) and was quenched with acetone
(20 mL). Crude reaction mixture was passed through silica gel
column, eluting with dichloromethane-pyridine mixture (100:1). All
green-purple fractions were collected, solvents were evaporated,
the residue was dissolved in dichloromethane-pyridine mixture
(95:5, 100 mL) and 200 mL of methanol was added to precipitate
brominated porphyrins. All crystals were collected by filtration
after 30 min to give a mixture of mono and dibrominated porphyrins
(ratio 2.3:1, 4.9 g, ca. 85%). This mixture was used for the next
step without further separation. B) A mixture of the above mono and
dibromoporphyrins (ratio of mono- to di-bromoporphyrins 2.3:1, 4 g,
ca. 4.7 mmol), cesium carbonate (7.8 g, 24 mmol, 5 equiv.),
Pd(PPh3)4 (271 mg, 5 mol %) and 1-pyrenyl-tetramethyldioxaborolane
(2.32 g, 7.1 mmol) in toluene (700 mL) was degassed and reflux in
nitrogen atmosphere for 12 h. Reaction mixture was cooled and
passed consecutively through pad of celite, silica gel and neutral
alumina washing with toluene. Toluene was distilled off in vacuum,
the residue was separated by fractional crystallization from
dichloromethane-methanol and column chromatography on silica gel
eluting with mixture of hexanes and ethyl acetate to afford
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)porphyrinato(2-)-.kappa.-
N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24) zinc(II)
(see FIG. 12, compound II) 2.76 g, 2, 9 mmol, 62%) and
[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-Bis(1-pyrenyl)porphyrinato(2-)-.-
kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)zinc(II)
(0.81 g, 0.71 mmol, 15%).
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)porphyrinato(2-)-.kappa.N-
.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)zinc(II)
(see FIG. 12, compound II)
[0109] .sup.1H-NMR (CDCl.sub.3, 400 MHz): 1.54 (s, 36H), 7.43 (d,
1H, J=9.3 Hz), 7.67 (d, 1H, J=9.3 Hz), 7.60 (s, 2H), 8.00-8.18 (m,
6H), 8.32 (t, 2H, J=7 Hz), 8.40 (d, 1H, J=9.1 Hz), 8.51 (d, 1H,
J=7.7 Hz), 8.63 (d, 2H, J=4.6 Hz), 8.82 (d, 1H, J=7.7 Hz), 8.95 (d,
2H, J=4.6 Hz), 9.18 (d, 2H, J=4.5 Hz), 9.46 (d, 2H, J=4.5 Hz),
10.33 (s, 1H). MALDI TOF: 950 (M.sup.+), requires 948.41 for
C.sub.64H.sub.60N.sub.4Zn.
[0110]
[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-Bis(1-pyrenyl)porphyrinato-
(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)zinc(-
II). .sup.1H-NMR (CDCl.sub.3, 400 MHz): 1.47, 1.477 and 1.481 (s,
36H, rotamers), 7.50 (dd, 2H, J=9.3, 10.6 Hz), 7.71-7.74 (m, 4H,
rotamers), 8.04-8.14 (m, 8H), 8.33 (t, 4H, J=7.2 Hz), 8.42 (d, 2H,
J=9.1 Hz), 8.54 (d, 2H, J=7.7 Hz), 8.63 (dd, 4H, J=0.8, 4.7 Hz),
8.86 (dd, 2H, J=2.8, 7.7 Hz), 8.92 (d, 4H, J=4.7 Hz). MALDI TOF:
1150 (M.sup.+), requires 1148.47 for C.sub.80H.sub.68N.sub.4Zn.
{.mu.-[10,10'-Bis(1-pyrenyl)-5,5',15,15'-tetrakis(3,5-di-tert-butylphenyl)-
-18,18',20,20'-dicyclo-2,2%
biporphyrinato(4-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa-
.N.sup.24,.kappa.N.sup.21',.kappa.N.sup.22',.kappa.N.sup.23',.kappa.N.sup.-
24']}dizinc(II) (see FIG. 12, compound III)
[0111] Porphyrin II (160 mg, 0.17 mmol), DDQ (191 mg, 0.82 mmol, 5
equiv.) and scandium(III) triflate (414 mg, 0.82 mmol, 5 equiv.)
were dissolved in toluene (300 mL) under nitrogen atmosphere and
the mixture was stirred at room temperature for 1 hour and heated
at reflux for additional 2 h. After cooling to room temperature the
mixture was passed consecutively through pad with silica gel (2
times) and pad with alumina (eluation with dichloromethane-pyridine
mixture 100:1). Solvents were evaporated in vacuum, the residue was
dissolved in dichloromethane-pyridine mixture (30 mL, 100:1) and
the product was precipitated by addition of 200 mL of methanol.
Yield 110 mg (0.058 mmol, 68%). .sup.1H-NMR (5% pyridine-d.sub.5 in
CDCl.sub.3, 400 MHz): 1.33 (s, 72H), 7.06 (s, 4H), 7.10 (d, 4H,
J=4.5 Hz), 7.38 (d, 4H, J=4.5 Hz), 7.47-7.61 (m, 12H), 7.67 (t, 2H,
J=9 Hz), 7.93 (t, 2H, J=8 Hz), 8.01 (d, 2H, J=7 Hz), 8.10 (d, 2H,
J=9 Hz), 8.16 (d, 4H, J=8 Hz), 8.25 (d, 2H, J=7 Hz), 8.31 (t, 2H,
J=8 Hz), 8.53 (s, 2H). .sup.13C-NMR (5% pyridine-d.sub.5 in
CDCl.sub.3, 75 MHz): 31.4, 34.6, 105.6, 117.8, 120.3, 122.1, 122.5,
124.1, 124.5, 124.8, 125.1, 125.9, 126.6, 126.7, 127.1, 127.4,
128.0, 128.1, 130.3, 130.6, 130.7, 131.0, 131.3, 131.9, 135.8,
136.9, 140.3, 148.2, 153.1, 153.36, 153, 44, 154.3. MALDI TOF:
1894.5 (M.sup.+), requires 1895.77 for
C.sub.128H.sub.114N.sub.8Zn.sub.2.
{.mu.-[9,10,9'10'-Bis(1,10-pyrenyl)-5,5',15,15'-tetrakis(3,5-di-tert-butyl-
phenyl)-18,18',20,20'-dicyclo-2,2%
biporphyrinato(4-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa-
.N.sup.24,.kappa.N.sup.21',.kappa.N.sup.22',.kappa.N.sup.23',.kappa.N.sup.-
24']}dizinc(II) (see FIG. 12, compound IV)
[0112] Zinc porphyrin dimer III (65 mg, 0.034 mmol) and anhydrous
iron(III) chloride (120 mg, 0.74 mmol, ca. 20 equiv.) were stirred
in anhydrous dichloromethane (50 mL) under nitrogen atmosphere for
2 h. Reaction mixture was quenched with pyridine (2 mL), washed
with water and passed consecutively through pad with silica gel and
neutral alumina eluting with dichloromethane to give solution of
the crude free base fused porphyrin dimer (MALDI TOF: 1763
(M.sup.+), requires 1764). Solution of zinc(II) acetate dihydrate
(200 mg) in methanol (10 mL) was added to the solution of free-base
dimer and the mixture was stirred for 2 h at room temperature.
Reaction mixture was washed with water, passed consecutively
through pad with silica gel and neutral alumina eluting with
dichloromethane. The residue after evaporation of dichloromethane
in vacuum was dissolved in dichloromethane (10 mL) and the product
was precipitated by addition of methanol (100 mL). Yield 40-50 mg
(62-77%). Fused pyrene-porphyrin dimer IV exhibits increased p-p
stacking even in solution, so that .sup.1H-NMR spectrum in 5%
solution of pyridine-d.sub.5 in CDCl.sub.3 or CD.sub.2Cl.sub.2
consists of very broad signals in aromatic region and only broad
signals of tert-butyl groups can be identified (see FIG. 13).
However, aggregation can be avoided by using 5% solution of
pyridine-d.sub.5 in benzene-d.sub.6 (see FIG. 13). .sup.1H-NMR (5%
pyridine-d.sub.5 in CDCl.sub.3, 400 MHz): tert-butyl protons 1.18
(s, 36H), 1.41 and 1.45 (s, 36H), aromatic protons as broad
singlets 6.95, 7.00, 7.04, 7.54, 7.57, 7.60, 7.97, 8.13, 8.32.
.sup.1H-NMR (5% pyridine-d.sub.5 in benzene-d.sub.6, 400 MHz): some
aromatic signals are overlapping with signal of benzene, 1.32 (s,
36H), 1.45 and 1.47 (s, 36H), 6.73 (s, 2H), 7.46-7.55 (m, 6H),
7.74-8.06 (m, 20H), 8.35 (d, 2H, J=4.5 Hz), 8.50 (s, 2H), 8.64 (d,
4H, J=2.7 Hz), 9.03 (d, 2H, J=8.3 Hz). MALDI TOF: 1890.1 (M.sup.+),
requires 1889.74 for C.sub.128H.sub.110N.sub.8Zn.sub.2.
Example 2
Double Fusion of 1-Substituted Anthracene Rings with Zinc Porphyrin
Dimer. (See FIG. 14, Compound VI)
2-(4,5-dimethoxyanthracen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
and
2-(4,5-dimethoxyanthracen-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborola-
ne
[0113] To a solution of a mixture of 1-bromo- and
9-bromo-4,5-dimethoxyanthracenes (ratio of 1- and 9-bromo-isomers
3:1, 7.0 g, 22.1 mmol) in toluene (300 mL) 7 mol % of
Cl.sub.2Pd(PPh.sub.3).sub.2 (1 g, 1.54 mmol), 5 equivalents of
picolineborane and 10 equivalents of triethylamine was added.
Reaction mixture was degassed with nitrogen and refluxed overnight.
Reaction mixture was quenched with water, toluene was distilled off
and the residue was subjected to column chromatography on silica
gel (gradient eluation with hexanes-ethyl acetate mixtures from 1:0
to 1000:5) to give
2-(4,5-dimethoxyanthracen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(2.3 g, 6.3 mmol, 29%) and
2-(4,5-dimethoxyanthracen-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(0.5 g, 1.4 mmol, 6.2%).
2-(4,5-dimethoxyanthracen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
[0114] .sup.1H-NMR (CDCl.sub.3, 250 MHz): 1.42 (s, 12H), 4.01 (s,
3H), 4.02 (s, 3H), 6.68 (dd, 2H, J=9.0, 8.0 Hz), 7.34 (t, 1H, J=9
Hz), 7.64 (d, 1H, J=9 Hz), 8.06 (d, 1H, J=8 Hz), 9.26 (s, 1H), 9.28
(s, 1H). MALDI TOF: 364 (M.sup.+), requires 364.18 for
C.sub.22H.sub.25BO.sub.4.
2-(4,5-dimethoxyanthracen-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
[0115] .sup.1H-NMR (CDCl.sub.3, 250 MHz): 1.54 (s, 12H), 4.03 (s,
6H), 6.68 (d, 2H, J=8 Hz), 7.37 (dd, 2H, J=8.0, 9.0 Hz), 7.93 (d,
2H, J=9 Hz), 9.37 (s, 1H). MALDI TOF: 364 (M.sup.+), requires
364.18 for C.sub.22H.sub.25BO.sub.4.
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4,5-dimethoxyanthracen-1-yl)porphyr-
inato(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)-
zinc(II) (see FIG. 14, compound V)
[0116] A mixture of the above mono and dibromoporphyrins (ratio of
mono- to di-bromoporphyrins 10:1, 1.38 g, ca. 1.78 mmol), cesium
carbonate (3 g, 8.9 mmol, 5 equiv.), Pd(PPh.sub.3).sub.4 (620 mg,
30 mol %) and dimethoxyanthracen-1-yl-tetramethyldioxaborolane
(0.95 g, 2.67 mmol, 1.5 equiv.) in toluene (500 ml) was degassed
and reflux in nitrogen atmosphere for 2 h. Reaction mixture was
cooled and passed consecutively through pad of celite, silica gel
and neutral alumina washing with toluene. Toluene was distilled off
in vacuum, the residue was separated by fractional crystallization
from dichloromethane-methanol and column chromatography on silica
gel eluting with mixture of hexanes and ethyl acetate to afford
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4,5-dimethoxyanthracen-1-yl)porphy-
rinato(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24-
)zinc(II) (FIG. 11, compound V) 1.35 g, 1.37 mmol, 77%) and
[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-Bis(4,5-dimethoxyanthracen-1-yl)-
porphyrinato(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.-
sup.24)zinc(II).
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4,5-dimethoxyanthracen-1-yl)porphyr-
inato(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)-
zinc(II) (see FIG. 14, compound V)
[0117] .sup.1H-NMR (5% pyridine-d.sub.5 in CDCl.sub.3, 400 MHz):
1.50 (d, 36H, J=1 Hz), 4.05 (s, 3H), 4.33 (s, 3H), 6.39 (d, 1H,
J=8.8 Hz), 6.47 (d, 1H, J=7.1 Hz), 6.91 (dd, 1H, J=7.1, 8.8 Hz),
7.36 (s, 1H), 7.74 (t, 2H, J=2 Hz), 8.02 (t, 2H, J=2 Hz), 8.10 (t,
2H, J=2 Hz), 8.14 (d, 1H, J=8 Hz), 8.68 (d, 2H, J=4.6 Hz), 8.82 (d,
2H, J=4.6 Hz), 9.06 (d, 2H, J=4.5 Hz), 9.33 (d, 2H, J=4.5 Hz), 9.49
(s, 1H), 10.14 (s, 1H). .sup.13C-NMR (5% pyridine-d.sub.5 in
CDCl.sub.3, 75 MHz): 31.0, 33.00, 33.02, 36.2, 56.1, 56.3, 100.0,
100.7, 104.6, 114.1, 116.6, 118.9, 119.1, 119.9, 122.4, 122.5,
123.7, 126.4, 128.3, 128.5, 129.5, 129.9, 130.4, 130.5, 130.7,
130.9, 131.4, 135.5, 140.4, 146.1, 146.2, 147.4, 148.0, 148.2,
148.7, 153.5, 153.6. MALDI TOF: 985.6 (M.sup.+), requires 984.43
for C.sub.64H.sub.64N.sub.4O.sub.2Zn.
{.mu.-[10,10'-Bis(4,5-dimethoxyanthracen-1,9-yl)-5,5',15,15'-tetrakis(3,5--
di-tert-butylphenyl)-18,18',20,20'-dicyclo-2,2'-biporphyrinato(4-)-.kappa.-
N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24,
.kappa.N.sup.21',.kappa.N.sup.22',.kappa.N.sup.23',.kappa.N.sup.24']}dizi-
nc(II) (see FIG. 14, compound VI)
[0118] Porphyrin V (50 mg, 0.051 mmol), DDQ (115 mg, 0.51 mmol, 10
equiv.) and scandium(III) triflate (249 mg, 0.51 mmol, 10 equiv.)
were dissolved in toluene (50 mL) under nitrogen atmosphere and the
mixture was stirred at room temperature for 1 h and heated at
reflux for additional 8 h. After cooling to room temperature the
mixture was passed consecutively through pad with silica gel (2
times) and pad with alumina (eluation with dichloromethane-pyridine
mixture 100:1). Solvents were evaporated in vacuum, the residue was
dissolved in dichloromethane-pyridine mixture (30 ml, 100:1) and
the product was precipitated by addition of 200 mL of methanol.
Yield 47 mg (0.23 mmol, 94%). Fused anthracene-porphyrin dimer VI
exhibits increased aggregation in solution, so that .sup.1H-NMR
spectrum in 5% solution of pyridine-d.sub.5 in CDCl.sub.3 consists
of broad signals in aromatic region and only broad signals of
tert-butyl groups can be identified. .sup.1H-NMR (5%
pyridine-d.sub.5 in CDCl.sub.3, 400 MHz): tert-butyl protons 1.43,
1.44 and 1.47 (s, 72H), broad singlets of methoxy group 3.97, 4.08
and 4.17, aromatic protons as broad signals 6.60 (m), 6.67 (d, J=8
Hz), 6.78 (d, J=7 Hz), 6.85 (s), 6.99 (t, J=9 Hz), 7.04 (s), 7.07
(d, J=8 Hz), 7.12 (d, J=9 Hz), 7.49 (s), 7.67 (s). .sup.13C-NMR (5%
pyridine-d.sub.5 in CDCl.sub.3, 75 MHz): 29.3, 31.1 (broad), 34.6
(broad), 52.2 (broad), 55.3 (broad), 122.2, 123.1, 123.2, 123.3,
125.5, 125.53, 126.0, 127.2, 127.7, 127.74, 127.9, 128.0, 128.3,
128.4, 128.5, 128.7, 129.8, 134.5, 135.5, 137.6, 138.5. MALDI TOF:
1963 (M.sup.+), requires 1963.78 for
C.sub.128H.sub.118N.sub.8O.sub.4Zn.sub.2. Absorption spectrum can
be seen in FIG. 11.
Example 3
Triple Fusion of 9-Substituted Anthracene Rings with Zinc Porphyrin
Dimer. (See FIG. 14, Compound VIII)
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4,5-dimethoxyanthracen-9-yl)porphyr-
inato(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)-
zinc(II) (see FIG. 14, Compound VII)
[0119] A) NBS (3.6 g, 20 mmol, 2.3 equiv.) was added to a stirred
solution of porphyrin I (see FIG. 12, compound I, 5 g, 6.7 mmol) in
dichloromethane (300 mL) and pyridine (5 mL) at -10.degree. C.
(NaCl/ice bath) under nitrogen atmosphere. Reaction mixture was
stirred at the same temperature for 10 min the was allowed to warm
to 0.degree. C. in 5 min (water bath) and was quenched with acetone
(20 mL). Crude reaction mixture was passed through silica gel
column, eluting with dichloromethane-pyridine mixture (100:1). All
green-purple fractions were collected, solvents were evaporated,
the residue was dissolved in dichloromethane-pyridine mixture
(95:5, 100 mL) and 200 mL of methanol was added to precipitate
brominated porphyrins. All crystals were collected by filtration
after 30 min to give dibrominated porphyrin (4.6 g, 5.03 mmol,
75%). B) The above dibromoporphyrin (0.82 g, 0.9 mmol), cesium
carbonate (1.64 g, 5 mmol, 5.6 equiv.), Pd(PPh.sub.3).sub.4 (205
mg, 20 mol %) and dimethoxyanthracen-9-yl-tetramethyldioxaborolane
(0.49 g, 1.35 mmol, 1.5 equiv.) in toluene (400 mL) was degassed
and heated to reflux for 10 min. After that Pd.sub.2(dba).sub.3
(164 mg, 20 mol %) and tri-tert-butylphosphine (4 ml of 10% wt
solution in hexanes) were added and reaction mixture continued to
reflux in nitrogen atmosphere for 2 h. Reaction mixture was cooled
and passed consecutively through pad of celite, silica gel and
neutral alumina washing with toluene. Toluene was distilled off in
vacuum, the residue was separated by fractional crystallization
from dichloromethane-methanol and column chromatography on silica
gel eluting with mixture of hexanes and ethyl acetate to afford
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4,5-dimethoxyanthracen-9-yl)porphy-
rinato(2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24-
)zinc(II) (see FIG. 14, compound VII) 127 mg, 0.13 mmol, 14%).
.sup.1H-NMR (5% pyridine-d.sub.5 in CDCl.sub.3, 400 MHz): 1.48 (s,
36H), 4.16 (s, 6H), 6.39 (d, 2H, J=9 Hz), 6.62 (d, 2H, J=7 Hz),
6.73 (dd, 2H, J=7, 9 Hz), 7.71 (t, 2H, J=2 Hz), 8.03 (d, 4H, J=2
Hz), 8.24 (d, 2H, J=4.6 Hz), 8.74 (d, 2H, J=4.6 Hz), 9.04 (d, 2H,
J=4.4 Hz), 9.32 (d, 2H, J=4.4 Hz), 9.73 (s, 1H), 10.15 (s, 1H).
.sup.13C-NMR (5% pyridine-d.sub.5 in CDCl.sub.3, 75 MHz): 31.7,
34.9, 55.6, 100.8, 105.6, 115.9, 116.3, 120.3, 121.2, 121.3, 123.6,
123.7, 125.1, 129.9, 131.1, 131.3, 132.3, 132.4, 135.8, 136.2,
136.8, 142.2, 148.1, 149.4, 149.7, 149.9, 150.4, 150.7, 155.7.
MALDI TOF: 985 (M.sup.+), requires 984.43 for
C.sub.64H.sub.64N.sub.4O.sub.2Zn.
{.mu.-[10,10'-Bis(4,5-dimethoxyanthracen-1,8,9-yl)-5,5',15,15%
tetrakis(3,5-di-tert-butylphenyl)-18,18',20,20'-dicyclo-2,2%
biporphyrinato(4-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa-
.N.sup.24,
.kappa.N.sup.21',.kappa.N.sup.22',.kappa.N.sup.23',.kappa.N.sup-
.24']}dizinc(II) (see FIG. 14, compound VI)
[0120] Porphyrin VII (20 mg, 0.051 mmol), DDQ (36 mg, 0.16 mmol, 8
equiv.) and scandium(III) triflate (79 mg, 0.16 mmol, 8 equiv.)
were dissolved in toluene (20 mL) under nitrogen atmosphere and the
mixture was stirred at room temperature for 1 h and heated at
reflux for additional 8 h. After cooling to room temperature the
mixture was passed consecutively through pad with silica gel (2
times) and pad with alumina (eluation with dichloromethane-pyridine
mixture 100:1). Yield 19 mg (quant.). Fused anthracene-porphyrin
dimer VIII exhibits increased aggregation in solution, so that
.sup.1H-NMR spectrum in 5% solution of pyridine-d.sub.5 in
CDCl.sub.3 consists of broad signals in aromatic region and could
not be resolved. MALDI TOF: 1959 (M.sup.+), requires 1957.75 for
C.sub.128H.sub.114N.sub.8O.sub.4Zn.sub.2. Absorption spectrum can
be seen in FIG. 11.
Example 4
Double Fusion of 3-Substituted Benzothienyl Rings with Zinc
Porphyrin Dimer
##STR00065##
[0121]
[10,20-Bis(3,5-di-tert-butylphenyl)-5-(3-benzothienyl)porphyrinato(-
2-)-.kappa.N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24)zinc(I-
I)
[0122] A mixture of the above mono and dibromoporphyrins (ratio of
mono- to di-bromoporphyrins 6:4, 1.0 g, ca. 1.1 mmol), cesium
carbonate (3 g, 8.9 mmol), Pd(PPh.sub.3).sub.4 (120 mg, 10 mol %),
pyridine (4 mL) water (2 mL) and 3-benzothienylboronic acid (0.39
g, 2.2 mmol, 2 equiv.) in toluene (400 mL) was degassed and reflux
in nitrogen atmosphere for 7 h. Reaction mixture was cooled and
passed consecutively through pad of celite, silica gel and neutral
alumina washing with toluene. Toluene was distilled off in vacuum,
the residue was crystallized by addition of methanol to
dichloromethane solution. Yield of mono and bis-substituted
3-benzothienyl porphyrins 1 g, used for the next step without
further purification.
##STR00066##
{.mu.-[9,10,9',10'-Bis(2,3-benzothienyl)-5,5',15,15'-tetrakis(3,5-di-tert-
-butylphenyl)-18,18',20,20'-dicyclo-2,2'-biporphyrinato(4-)-.kappa.N.sup.2-
1,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.24,.kappa.N.sup.21',.kappa.-
N.sup.22',.kappa.N.sup.23',.kappa.N.sup.24']}dizinc(II)
[0123] A mixture of above benzothienyl-substituted porphyrins (1.0
g, 0.68 mmol), DDQ (770 mg, 3.4 mmol, 5 equiv.) and scandium(III)
triflate (1670 mg, 3.4 mmol, 5 equiv.) were dissolved in toluene
(500 mL) under nitrogen atmosphere and the mixture was stirred at
room temperature for 1 h and heated at reflux for additional 1 h.
After cooling to room temperature the mixture was subjected to
column chromatography eluting with a mixture of
hexanes-dichloromethane-pyridine. Solvents were evaporated in
vacuum, the residue was dissolved in dichloromethane-pyridine
mixture (30 mL, 100:1) and the product was precipitated by addition
of 200 mL of methanol. Yield 170 mg (0.1 mmol, 15%). Fused
anthracene-porphyrin dimer VI exhibits increased aggregation in
solution, so that 1H-NMR spectrum in 5% solution of pyridine-d5 in
CDCl3 consists of broad signals in aromatic region and only broad
signals of tert-butyl groups can be identified. UV/VIS (2% C5H5N in
CH2Cl2) .lamda., nm: 1485, 1186, 768, 670, 617, 433. (MALDI TOF:
1833.3 (M+), requires 1832.67 (100%) for
C.sub.128H.sub.118N.sub.8O.sub.4Zn.sub.2*C.sub.5H.sub.5N.
##STR00067##
{.mu.-[9,10,9'10'-Bis(1,10-pyrenyl)-5,5',15,15%
tetrakis(3,5-di-tert-butylphenyl)-18,18',20,20'-dicyclo-2,2%
biporphyrinato(4-)-N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.-
24,N.sup.21',.kappa.N.sup.22',.kappa.N.sup.23',.kappa.N.sup.24']}dilead(II-
)
[0124] Fully fused zinc porphyrin dimer III (50 mg, 0.026 mmol) was
dissolved in dichloromethane (10 mL), conc. hydrochloric acid (0.2
mL) was added and the reaction mixture was vigorously stirred for 1
min. Reaction mixture was quenched with pyridine (0.5 mL), washed
with water and passed consecutively through pad with silica gel and
neutral alumina eluting with dichloromethane to give solution of
the free base fused porphyrin dimer (MALDI TOF (100% int): 1763
(M+), requires 1764). Solution of lead(II) acetate trihydrate (100
mg) in pyridine (4 mL) was added to the solution of free-base dimer
and the mixture was heated to reflux for 3 h. After that the
reaction mixture was cooled to room temperature and passed
consecutively through pad with silica gel and neutral alumina
eluting with dichloromethane. The residue after evaporation of
solvents in vacuum was dissolved in dichloromethane (1 mL) and the
product was precipitated by addition of methanol (10 mL). Yield 43
mg (0.020 mmol, 76%). .sup.1H-NMR (5% pyridine-d5 in benzene-d6,
400 MHz, recorded at 75.degree. C.) consists of broad signals due
to: 1.33 (br. s, 36H), 1.53 (br. s, 36H), 7.04 (br. t, 2H, J=4.5
Hz), 7.63 (br. t, 2H, J=4.5 Hz), 7.69-8.23 (m), 8.57 (br. s, 2H),
8.92 (br. s, 2H). MALDI TOF (100% int): 2174.73 (M+), requires
2175.84 for C.sub.128H.sub.110N.sub.8Pb.sub.2. UV/VIS NIR (1%
C.sub.5H.sub.5N in CH.sub.2Cl.sub.2), .lamda., (.epsilon.): 1459
(63583), 1241 (26596), 634 (141820), 476 (33718), 426 (36312).
##STR00068##
{.mu.-[9,10,9'10'-Bis(1,10-pyrenyl)-5,5',15,15%
tetrakis(3,5-di-tert-butylphenyl)-18,18',20,20'-dicyclo-2,2%
biporphyrinato(4-)-N.sup.21,.kappa.N.sup.22,.kappa.N.sup.23,.kappa.N.sup.-
24,N.sup.21',.kappa.N.sup.22',.kappa.N.sup.23',.kappa.N.sup.24']}tetrachlo-
roditin(II)
[0125] Fully fused zinc porphyrin dimer III (50 mg, 0.026 mmol) was
dissolved in dichloromethane (10 mL), conc. hydrochloric acid (0.2
mL) was added and the reaction mixture was vigorously stirred for 1
min. Reaction mixture was quenched with pyridine (0.5 mL), washed
with water and passed consecutively through pad with silica gel and
neutral alumina eluting with dichloromethane to give solution of
the free base fused porphyrin dimer (MALDI TOF (100% int): 1763
(M+), requires 1764). Solution of tin(II) chloride trihydrate (200
mg) in pyridine (5 mL) was added to the solution of free-base dimer
in chloroform (100 mL) and the mixture was heated to reflux for 2
h. After that the reaction mixture was cooled to room temperature,
washed with water (100 mL) and passed consecutively through pad
with silica gel eluting with dichloromethane. The residue after
evaporation of solvents in vacuum was dissolved in dichloromethane
(10 mL) and the product was precipitated by addition of methanol
(50 mL). Yield 35 mg (0.016 mmol, 63%). .sup.1H-NMR (5% pyridine-d5
in benzene-d6, 400 MHz, recorded at 75.degree. C.) consists of
broad signals due to aggregation. MALDI TOF (100% int): 2066.9
(100%, M+-2Cl), 2139.1 (M+), requires 2067.63 for
C.sub.128H.sub.110N.sub.8Sn.sub.2Cl.sub.2 (M-2Cl), 2139.57 for
C.sub.128H.sub.110N.sub.8Sn.sub.2Cl.sub.4(M+).
Device Examples
[0126] While few examples have been demonstrated, near-infrared
(NIR) organic photodetectors with response at wavelengths (X)
beyond the cutoff of Si (i.e. .lamda.>1100 nm) are interesting
for use in imaging and other detection applications. (A. Rogalski,
Infrared Physics & Technology 2002, 43, 187). In previous work,
polymer photodetectors with response at .lamda.>1000 nm have
been demonstrated, but the optical sensitivity is generally due to
a long absorption tail having an external quantum efficiency (EQE)
less than a few percent. (Y. J. Xia, L. Wang, X. Y. Deng, D. Y. Li,
X. H. Zhu, Y. Cao, Applied Physics Letters 2006, 89; L. Wen, B. C.
Duck, P. C. Dastoor, S. C. Rasmussen, Macromolecules 2008, 41,
4576; and E. Perzon, F. L. Zhang, M. Andersson, W. Mammo, O.
Inganas, M. R. Andersson, Advanced Materials 2007, 19, 3308).
Organic materials systems with a large NIR photoresponse are rare
for several reasons. A type-II (staggered) heterojunction must be
formed between the donor and acceptor materials with a sufficient
energy offset to dissociate photogenerated excitons; as the
energy-gap is decreased, finding molecular combinations with
suitable energy alignments becomes increasingly difficult. In
addition, exciton lifetimes generally decrease with energy gap due
to exciton-phonon induced recombination (i.e. internal conversion).
(H. S. Cho, D. H. Jeong, S. Cho, D. Kim, Y. Matsuzaki, K. Tanaka,
A. Tsuda, A. Osuka, Journal of the American Chemical Society 2002,
124, 14642; D. Tittelbachhelmrich, R. P. Steer, Chemical Physics
1995, 197, 99). These difficulties have motivated the development
of hybrid organic-inorganic devices using polymeric and
small-molecule materials in conjunction with II-VI quantum dots
(with EQE<1% at .lamda.>1000 nm) (X. M. Jiang, R. D.
Schaller, S. B. Lee, J. M. Pietryga, V. I. Klimov, A. A. Zakhidov,
Journal of Materials Research 2007, 22, 2204) or single walled
carbon nanotubes (EQE.apprxeq.2% at .lamda.=1150 and 1300 nm) (M.
S. Arnold, J. D. Zimmerman, C. K. Renshaw, X. Xu, R. R. Lunt, C. M.
Austin, S. R. Forrest, Nano Letters 2009, 9, 3354). Here, we
demonstrate a NIR having EQE=6.5% at .lamda.=1350 nm using
photodetectors based on triplylinked porphyrin-tape dimers. These
porphyrin tapes are representative of a promising new class of
materials that can be modified to exhibit even longer wavelength
response by spatially extending the conjugation of the electron
system (H. S. Cho, D. H. Jeong, S. Cho, D. Kim, Y. Matsuzaki, K.
Tanaka, A. Tsuda, A. Osuka, Journal of the American Chemical
Society 2002, 124, 14642).
[0127] The molecules provided consist of a base of two
Zn-metallated porphyrins, triplylinked at the meso-meso and both
.beta.-.beta. positions, with four side groups of
3,5-di-tert-butylphenyl, but differ in the end-terminations of
singly bonded 4-cyanophenyl (CNPh), 3,5-di-tertbutyl-phenyl
(DTBPh), pyrene (Psub), and doubly-bonded pyrene (Pfused) (see
inset, FIG. 15). The triply-fused porphyrin tapes were synthesized
as described previously. (A. Tsuda, H. Furuta, A. Osuka, Angewandte
Chemie International Edition 2000, 39, 2549; M. Kamo, A. Tsuda, Y.
Nakamura, N. Aratani, K. Furukawa, T. Kato, A. Osuka, Organic
Letters 2003, 5, 2079; F. Y. Cheng, S. Zhang, A. Adronov, L.
Echegoyen, F. Diederich, Chemistrya European Journal 2006, 12,
6062). Psub was converted to Pfused by a procedure similar to that
reported by Osuka, et. al. (K. Kurotobi, K. S. Kim, S. B. Noh, D.
Kim, A. Osuka, Angewandte Chemie International Edition 2006, 45,
3944). The compounds absorb throughout the visible and into the
NIR, with Q-band absorption peaks between wavelengths of .lamda.
1050 nm and 1350 nm, and have corresponding absorption coefficients
of <=1.5-3.times.10.sup.4 cm.sup.-1, as shown in FIG. 4. Films
for materials characterization were deposited on bare, or
poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOT-PSS)
coated quartz substrates using a film casting knife (i.e. a doctor
blade). An atomic force microscope (AFM) was used to measure
surface morphology. CNPh was soluble (5-10 mg/ml) in pure
chlorobenzene, and as shown in FIG. 16(a), formed large crystalline
domains with >20 nm root mean square (RMS) roughness that proved
too rough for device fabrication. The addition of 1 (vol) %
pyridine to CNPh enhanced its solubility, thereby decreasing the
RMS roughness to 9.0 nm, and changed the film morphology from
large, cracked oak leaf-shaped grains to almond-shaped grains as
shown in FIG. 16(b). Both DBTPh and Psub were more soluble than
CNPh (>10 mg/ml) in chlorobenzene, and formed films with 0.5 nm
and 2.7 nm RMS roughness, respectively (FIGS. 16(c) and (d)). The
solubility of Pfused was <2.5 mg/ml in chlorobenzene, resulting
in a thin (and hence overly transparent) film; the addition of 1
(vol) % pyridine increased solubility and resulted in films with a
RMS roughness of 5.3 nm.
[0128] X-ray diffraction peaks (see FIG. 17a) were observed at
2.theta.=4.21.+-.0.1.degree. for CNPh cast from chlorobenzene,
4.28.+-.0.1.degree. for CNPh cast from chlorobenzene with 1 (vol) %
pyridine, and 4.34.+-.0.1.degree. for Psub, corresponding to the
distance between the (001) planes of 20.96.+-.0.50 .ANG.,
20.62.+-.0.48 .ANG., and 20.32.+-.0.47 .ANG., respectively. These
closely match the calculated (001) interplanar spacing of 20.2
.ANG. and 20.0 .ANG. for CNPh and Psub, respectively, as seen in
the calculated crystal structure shown in FIG. 17(b). The lone
(001) diffraction peak indicates that the molecules crystallize
with their (001)-planes parallel to the substrate surface. The
addition of pyridine increases the fullwidth half-maximum (FWHM) of
the CNPh diffraction peak from 0.214.+-.0.004.degree. (2.theta.) to
0.463.+-.0.010.degree. (2.theta.), corresponding to Scherrer
broadening due to mean crystallite sizes of 43.+-.2 nm (.about.20
molecular layers) and 18.+-.1 nm (.about.9 molecular layers),
respectively. (A. Guinier, Xray diffraction in crystals, imperfect
crystals, and amorphous bodies, W.H. Freeman, San Francisco, 1963).
The FWHM for Psub is 0.354.+-.0.010.degree. (2.theta.),
corresponding to a crystallite size of 24.+-.1 nm (.about.12
molecular layers). No diffraction peaks are observed for DTBPh or
Pfused, indicating that the films are amorphous. The reduction and
oxidation potentials of Psub and Pfused were measured against a
ferrocene/ferricinium reference. The reduction (oxidation)
potentials for Psub and Pfused are -1.10 V (-0.01 V) and -0.97 V
(-0.13 V), respectively. Reduction (oxidation) potentials for
DTBPh, CNPh, and C60 have previously been measured at -1.07 V
(+0.03 V) and -1.07 V (0.01V), and -0.86 V, respectively. (L. A.
Fendt, H. Fang, M. E. Plonska-Brzezinska, S. Zhang, F. Cheng, C.
Braun, L. Echegoyen, F. Diederich, European Journal of Organic
Chemistry 2007, 4659; S. A. Lerke, B. A. Parkinson, D. H. Evans, P.
J. Fagan, Journal of the American Chemical Society 1992, 114,
7807). Devices were fabricated on pre-cleaned PEDOT-PSS-coated
indium tin oxide (ITO)-on-glass substrates using the same
conditions as for the morphological studies, followed by sequential
vacuum thermal evaporation (VTE) of C.sub.60, bathocuproine (BCP),
and the Ag cathodes. Rectification ratios of >2.times.10.sup.3
at .+-.1 V were observed for CNPh, DTBPh, and Pfused, and
>2.times.10.sup.6 for Psub devices. Ideality factors of
n.apprxeq.1.3 were observed for all devices except those based on
CNPh, where n.apprxeq.1.8, as shown in FIG. 18. An ideality of
n<1.5 is typical of drift-diffusion, and a ideality between
n=1.5 and n=2 is characteristic of defect assisted
generation-recombination in the bulk or at the donor-acceptor
heterointerface. Defect-related traps may arise from the presence
of impurities or morphological disorder. (N. Li, B. E. Lassiter, R.
R. Lunt, G. Wei, S. R. Forrest, Applied Physics Letters 2009, 94,
3). When converting Psub to Pfused, the process of forming the
additional bond to the pyrene end group decreases the reduction
potential of Psub, therefore decreasing the interfacial gap (i.e.
the energy difference between the highest occupied molecular
orbital, or HOMO, of the porphyrin tape molecule, and the lowest
unoccupied molecular orbital, or LUMO, of C.sub.60) by 0.12 eV,
leading to a calculated 11-fold increase in interface-generated
dark current (B. P. Rand, D. P. Burk, S. R. Forrest, Physical
Review B 2007, 75, 11) compared with an observed difference of
approximately three orders of magnitude. These differences suggest
that an increased generation-recombination rate from defects is
present in the CNPh and Pfused materials, as compared to DTBPh and
Psub. Alternatively, the bulky end groups of Psub and DTBPh reduce
the interaction between the donor and acceptor systems resulting in
a reduced geminate recombination rate and thus a lower dark current
in respect to the CNPh and Pfused with the less bulky end groups.
(M. D. Perez, C. Borek, S. R. Forrest, M. E. Thompson, Journal of
the American Chemical Society 2009, 131, 9281).
[0129] Spectrally resolved EQE for the several devices are shown in
FIG. 19. Peak efficiencies of 1.2.+-.0.1%, 1.6.+-.0.1%,
2.1.+-.0.1%, and 6.5.+-.0.3% at wavelengths of .lamda.=1045 nm,
1130 nm, 1090 nm, and 1345 nm are observed for TBPh-, CNPh-, Psub-,
and Pfused-based devices, respectively. A transfer matrix model was
used to determine the internal quantum efficiency (IQE) from the
EQE data and the optical properties of the device structures. (P.
Peumans, A. Yakimov, S. R. Forrest, Journal of Applied Physics
2003, 93, 3693). In a structure consisting of a 20.+-.4 nm-thick
film of Pfused, 125 nm of C60, 10 nm of BCP, and 100 nm of Ag,
19.+-.5% of the incident radiation at .lamda.=1350 nm light is
absorbed, while the observed EQE was 5.9%. This results in
IQE=31.+-.8%, indicating that excitons are collected from an active
region thickness of 6.2.+-.1.6 nm. Films cast from solutions of
0.25, 0.5, and 1 mg/ml in chlorobenzene resulted in thicknesses of
20.+-.4 nm, 60.+-.12 nm, and 120.+-.24 nm, resulting in
EQE=5.3.+-.0.6%, 6.2.+-.0.4%, and 4.5.+-.0.4% at .lamda.=1350 nm,
respectively. The weak dependence on donor-layer thickness is
consistent with a diffusion length smaller than the thinnest
film.
[0130] The specific detectivity is calculated using:
D*=A1/2/S.sub.N, where is the responsivity, A is the detector
active area, and S.sub.N is the RMS noise current spectral density.
(S. M. Sze, Physics of Semiconductor Devices, Wiley, New York 1981,
xii). Peak specific detectivities at zero bias, where thermal noise
dominates, of D*=1.6.+-.0.1.times.10.sup.11 Jones at .lamda.=1090
nm for Psub-, and 2.3.+-.0.1.times.10.sup.10 Jones at .lamda.=1350
nm for Pfused-based devices were obtained, as shown in FIG. 19.
These detectivities are significantly less than for InGaAs
detectors (.about.10.sup.13 Jones) that are sensitive within the
same wavelength range, but are comparable to those obtained using
cooled PbS detectors. (A. Rogalski, Infrared Physics &
Technology 2002, 43, 187; J. G. Webster, The measurement,
instrumentation, and sensors handbook, CRC Press published in
cooperation with IEEE Press, Boca Raton, Fla. 1999).
[0131] The electrical response to optical excitation using an
external 50.OMEGA. load was used to probe photogenerated carrier
extraction and device bandwidth, with results shown in FIG. 6. For
Psub-based detectors, the response decay time constant is
2.09.+-.0.02 ns at V=0, decreasing asymptotically to
.tau.=1.87.+-.0.03 ns at -1 V. This corresponds to 3 dB roll-off
frequency of 56.+-.7 MHz as shown in FIG. 20, inset. At -1V, the
response times of Pfused-, DTBPh-, and CNPh-based devices are
.tau.=2.15.+-.0.02 ns, 2.30.+-.0.02 ns, and 3.17.+-.0.02 ns,
respectively. The capacitances of the devices are between C=20.4
and 21.6 nF/cm2, indicating fully depleted active regions that
should have resistance-capacitance (RC) time constants of
.about.0.8 ns across a 50.OMEGA. load, assuming series resistance
is negligible. Here, .tau. was found to decrease when either the
C.sub.60 and/or the porphyrin dimer thickness was increased, thus
decreasing capacitance, indicating that parasitic series resistance
introduces a limit to the device bandwidth.
[0132] Therefore, these porphyrin tape molecules may be promising
for use in NIR photodetector applications. By extending the
conjugation length in this broad class of materials, the absorption
is extended from the near visible deep into the NIR. The detector
performance is influenced by the functionalizing substituent
molecule that, in turn, affects the film crystal structure and
morphology. Detectors based on the Pfused, have a peak EQE=6.5%,
D*=2.3.+-.0.1.times.1010 Jones, and a response time of
.tau.=2.12.+-.0.02 ns at .lamda.=1350 nm.
[0133] It is understood that the various embodiments described
herein are by way of example only, and are not intended to limit
the scope of the invention. For example, many of the materials and
structures described herein may be substituted with other materials
and structures without deviating from the spirit of the invention.
The present invention as claimed may therefore includes variations
from the particular examples and preferred embodiments described
herein, as will be apparent to one of skill in the art. It is
understood that various theories as to why the invention works are
not intended to be limiting.
* * * * *