U.S. patent application number 12/480310 was filed with the patent office on 2009-10-01 for charge transport compositions and electronic devices made with such compositions.
This patent application is currently assigned to E.I. DU PONT DE NEMOURS AND COMPANY. Invention is credited to Mark A. Guidry, Norman Herron, Daniel David Lecloux, Nora Sabina Radu, Eric Maurice Smith, Ying Wang.
Application Number | 20090242837 12/480310 |
Document ID | / |
Family ID | 30118439 |
Filed Date | 2009-10-01 |
United States Patent
Application |
20090242837 |
Kind Code |
A1 |
Herron; Norman ; et
al. |
October 1, 2009 |
CHARGE TRANSPORT COMPOSITIONS AND ELECTRONIC DEVICES MADE WITH SUCH
COMPOSITIONS
Abstract
The present invention relates to charge transport compositions.
The invention further relates to electronic devices in which there
is at least one active layer comprising such charge transport
compositions.
Inventors: |
Herron; Norman; (Newark,
DE) ; Guidry; Mark A.; (Wilmington, DE) ;
Lecloux; Daniel David; (Wilmington, DE) ; Radu; Nora
Sabina; (Landenberg, PA) ; Smith; Eric Maurice;
(Hockessin, DE) ; Wang; Ying; (Wilmington,
DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1122B, 4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Assignee: |
E.I. DU PONT DE NEMOURS AND
COMPANY
Wilmington
DE
|
Family ID: |
30118439 |
Appl. No.: |
12/480310 |
Filed: |
June 8, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11676401 |
Feb 19, 2007 |
7544312 |
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12480310 |
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10612244 |
Jul 2, 2003 |
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11676401 |
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60394767 |
Jul 10, 2002 |
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60458277 |
Mar 28, 2003 |
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Current U.S.
Class: |
252/301.16 |
Current CPC
Class: |
C07D 401/04 20130101;
H01L 51/0072 20130101; C09B 11/10 20130101; H01L 51/0035 20130101;
H01L 51/0059 20130101; H01L 51/0068 20130101; H01L 51/0085
20130101; H01L 51/0081 20130101; C07C 211/49 20130101; C07D 403/04
20130101; C07D 209/86 20130101; H01L 51/5012 20130101; C07C 211/52
20130101; C07D 471/14 20130101; C09K 2211/185 20130101; C07D 213/38
20130101; Y10S 428/917 20130101; H01L 51/5016 20130101; C08G 61/122
20130101; C08L 65/00 20130101; C09K 2211/1044 20130101; C07D 241/38
20130101; H01L 51/5048 20130101; H01L 2251/308 20130101; C07C
211/54 20130101; H01L 51/0094 20130101; C07D 241/42 20130101; H01L
51/005 20130101; H01L 51/0067 20130101; C07D 475/00 20130101; H01L
51/0043 20130101; C07D 487/04 20130101; C07C 217/80 20130101; C07D
401/14 20130101; C07D 409/04 20130101; H01L 51/0071 20130101; H01L
51/0065 20130101; C07C 215/74 20130101; C07F 7/0838 20130101; C07D
471/04 20130101; H01L 51/0062 20130101; H05B 33/14 20130101; C07C
255/58 20130101; H01L 51/50 20130101; C07D 409/14 20130101; C09K
11/06 20130101; C08G 61/124 20130101 |
Class at
Publication: |
252/301.16 |
International
Class: |
C09K 11/06 20060101
C09K011/06 |
Claims
1. An electronic device comprising at least one layer comprising a
charge transport composition having at least two triarylmethane
carbons, said composition having Formula II in FIG. 2, wherein:
Ar.sup.1 can be the same or different at each occurrence and is
selected from aryl and heteroaryl; R.sup.1 is the same or different
at each occurrence and is selected from H, alkyl, heteroalkyl,
aryl, heteroaryl, arylalkylene, heteroarylalkylene,
C.sub.nH.sub.aF.sub.b, and C.sub.6H.sub.cF.sub.d; R.sup.2 is the
same or different at each occurrence and is selected from arylene,
heteroarylene, arylenealkylene, and heteroarylenealkylene, with the
proviso that when R.sup.2 is arylenealkylene or
heteroarylenealkylene, an arylene end is attached to the
triarylmethane carbon; Q is selected from a single bond and a
multivalent group; m is an integer equal to at least 2; and p is 0
or 1, with the proviso that when p is 0, Q is a multivalent group
that is arylene or heteroarylene.
2. The device of claim 1 wherein Q is selected from a hydrocarbon
group with at least two points of attachment, selected from an
aliphatic group, a heteroaliphatic group, an aromatic group, and a
heteroaromatic group.
3. The device of claim 2 wherein Q is selected from alkyl groups,
heteroalkyl groups, alkenyl groups, heteroalkenyl groups, alkynyl
groups, and heteroalkynyl groups.
4. The device of claim 1 wherein Q is selected from single-ring
aromatic groups, multiple-ring aromatic groups, fused-ring aromatic
groups, single-ring heteroaromatic groups, multiple-ring aromatic
groups, fused-ring aromatic groups, arylamines, silanes and
siloxanes.
5. The device of claim 1, wherein Q is selected from Formulae
III(a) through III(h) in FIG. 4.
6. The device of claim 1 wherein Ar.sup.1 is selected from phenyl,
substituted phenyl, biphenyl, and substituted biphenyl.
7. The device of claim 6 wherein Ar.sup.1 is selected from
substituted phenyl and substituted biphenyl having at least one
substituent selected from alkyl, heteroalkyl, aryl, heteroaryl,
arylalkylene, heteroarylalkylene, C.sub.nH.sub.aF.sub.b, and
C.sub.6H.sub.cF.sub.d, where a, b, c, and d are 0 or an integer,
such that a+b=2n+1, and c+d=5, and n is an integer.
8. The device of claim 1 wherein Ar.sup.1 is selected from phenyl,
substituted phenyl, biphenyl, and substituted biphenyl, wherein at
least one carbon atom is replaced with a heteroatom.
9. The device of claim 1 wherein R.sup.2 is selected from phenyl,
substituted phenyl, biphenyl, substituted biphenyl, pyridyl,
substituted pyridyl, bipyridyl, and substituted bipyridyl.
10. The device of claim 9 wherein R.sup.2 is selected from
substituted phenyl, substituted biphenyl, and substituted pyridyl,
having at least one substituent selected from heteroalkyl, aryl,
heteroaryl, arylalkylene, heteroarylalkylene,
C.sub.nH.sub.aF.sub.b, and C.sub.6H.sub.cF.sub.d, where a, b, c,
and d are 0 or an integer, such that a+b=2n+1, and c+d=5, and n is
an integer.
11. The device of claim 1, wherein the charge transport composition
is selected from Formula II(a) through Formula II(f) in FIG.
12. The device of claim 1, wherein at least one N(R.sup.1).sub.2 is
a fused heteroaromatic ring group.
13. The device of claim 12, wherein at least one N(R.sup.1).sub.2
is selected from N-carbazoles, benzodiazoles, and
benzotriazoles.
14. The device of claim 1, wherein at least one X is a fused
heteroaromatic ring group.
15. The device of claim 14, wherein at least one X is selected from
N-carbazoles, benzodiazoles, and benzotriazoles.
16. An electronic device comprising at least one layer comprising a
charge transport composition selected from Formula II in FIG. 2,
wherein: Q is selected from a single bond and a multivalent group;
m is an integer from 2 through 10; Ar.sup.1 can be the same or
different at each occurrence and is selected from aryl and
heteroaryl; R.sup.1 is the same or different at each occurrence and
is selected from H, alkyl, heteroalkyl, aryl, heteroaryl,
C.sub.nH.sub.aF.sub.b, and C.sub.6H.sub.cF.sub.d; and R.sup.2 is
the same or different at each occurrence and is selected from
arylene, heteroarylene, arylenealkylene, and heteroarylenealkylene,
with the proviso that when R.sup.2 is arylenealkylene or
heteroarylenealkylene, an arylene end is attached to the
triarylmethane carbon.
17. The device of claim 16 wherein Q is selected from Formulae
III(a) through III(h) in FIG. 4.
18. The device of claim 16 wherein the charge transport composition
is selected from Formula II(a), Formula II(b), and Formula II(c) in
FIG. 5.
19. A device of claim 16, wherein the device is a light-emitting
diode, light-emitting electrochemical cell, or a photodetector.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. application Ser. No.
11/676,401, allowed, which is a division of U.S. application Ser.
No. 10/612,244 filed Jul. 2, 2003, and claims priority from U.S.
Provisional Application Ser. No. 60/394,767, filed Jul. 10, 2002,
and U.S. Provisional Application Ser. No. 60/458,277, filed Mar.
28, 2003, both of which are incorporated by reference herein in
their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to charge transport
compositions. The invention further relates to photoactive
electronic devices in which there is at least one active layer
comprising such charge transport compositions.
[0004] 2. Background
[0005] In organic photoactive electronic devices, such as
light-emitting diodes ("OLED"), that make up OLED displays, the
organic active layer is sandwiched between two electrical contact
layers in an OLED display. In an OLED the organic photoactive layer
emits light through the light-transmitting electrical contact layer
upon application of a voltage across the electrical contact
layers.
[0006] It is well known to use organic electroluminescent compounds
as the active component in light-emitting diodes. Simple organic
molecules, conjugated polymers, and organometallic complexes have
been used.
[0007] Devices which use photoactive materials, frequently include
one or more charge transport layers, which are positioned between
the photoactive (e.g., light-emitting) layer and one of the contact
layers. A hole transport layer may be positioned between the
photoactive layer and the hole-injecting contact layer, also called
the anode. An electron transport layer may be positioned between
the photoactive layer and the electron-injecting contact layer,
also called the cathode.
[0008] There is a continuing need for charge transport
materials.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a charge transport
composition comprising a triarylmethane having Formula I, shown in
FIG. 1, wherein: [0010] Ar.sup.1 can be the same or different at
each occurrence and is selected from aryl and heteroaryl; [0011]
R.sup.1 can be the same or different at each occurrence and is
selected from H, alkyl, heteroalkyl, aryl, heteroaryl,
arylalkylene, heteroarylalkylene, C.sub.nH.sub.aF.sub.b, and
C.sub.6H.sub.cF.sub.d; or adjacent R.sup.1 groups can be joined to
form 5- or 6-membered rings; [0012] X can be the same or different
at each occurrence and is selected from R.sup.1, alkenyl, alkynyl,
N(R.sup.1).sub.2, OR.sup.1, OC.sub.nH.sub.aF.sub.b,
OC.sub.6H.sub.cF.sub.d, halide, NO.sub.2, OH, CN, and COOR.sup.1;
[0013] n is an integer, and [0014] a, b, c, and d are 0 or an
integer such that a+b=2n+1, and c+d=5.
[0015] In another embodiment, the present invention is directed to
a charge transport composition comprising the above triarylmethane,
with the proviso that there is at least one substituent on an
aromatic group selected from F, C.sub.nH.sub.aF.sub.b,
OC.sub.nH.sub.aF.sub.b, C.sub.6H.sub.cF.sub.d, and
OC.sub.6H.sub.cF.sub.d.
[0016] In another embodiment, the present invention is directed to
a charge transport composition with at least one triarylmethane
carbon, having Formula II shown in FIG. 2, wherein: [0017] R.sup.2
is the same or different at each occurrence and is selected from
arylene, heteroarylene, arylenealkylene, and heteroarylenealkylene,
with the proviso that when R.sup.2 is arylenealkylene or
heteroarylenealkylene, an arylene end is attached to the
triarylmethane carbon; [0018] Q is selected from a single bond and
a multivalent group; [0019] m is an integer equal to at least 2;
[0020] p is 0 or 1, with the proviso that when p is 0, Q is a
multivalent group that is arylene or heteroarylene; and [0021]
Ar.sup.1, R.sup.1, a through d, and n are as defined above.
[0022] In another embodiment, the present invention is directed to
an electronic device having at least one layer comprising a
material selected from Formulae I and II, shown in FIGS. 1 and 2,
wherein Ar.sup.1, R.sup.1, R.sup.2, Q, X, a through d, m, n, and p
are as defined above, with the proviso that in Formula I when
X.sub.5Ar.sup.1 is p-methylphenylene, R.sup.1 is not ethyl.
[0023] As used herein, the term "charge transport composition" is
intended to mean material that can receive a charge from an
electrode and facilitate its movement through the thickness of the
material with relatively high efficiency and small loss of charge.
Hole transport compositions are capable of receiving a positive
charge from an anode and transporting it. Electron transport
compositions are capable of receiving a negative charge from a
cathode and transporting it. The term "anti-quenching composition"
is intended to mean a material which prevents, retards, or
diminishes both the transfer of energy and the transfer of an
electron to or from the excited state of the photoactive layer to
an adjacent layer. The term "photoactive" refers to any material
that exhibits electroluminescence, photoluminescence, and/or
photosensitivity. The term "HOMO" refers to the highest occupied
molecular orbital of a compound. The term "LUMO" refers to the
lowest unoccupied molecular orbital of a compound. The term "group"
is intended to mean a part of a compound, such as a substituent in
an organic compound. The prefix "hetero" indicates that one or more
carbon atoms has been replaced with a different atom. The term
"alkyl" is intended to mean a group derived from an aliphatic
hydrocarbon having one point of attachment, which group may be
unsubstituted or substituted. The term "heteroalkyl" is intended to
mean a group derived from an aliphatic hydrocarbon having at least
one heteroatom and having one point of attachment, which group may
be unsubstituted or substituted. The term "alkylene" is intended to
mean a group derived from an aliphatic hydrocarbon and having two
or more points of attachment. The term "heteroalkylene" is intended
to mean a group derived from an aliphatic hydrocarbon having at
least one heteroatom and having two or more points of attachment.
The term "alkylene" is intended to mean a group derived from an
aliphatic hydrocarbon and having two or more points of attachment.
The term "heteroalkylene" is intended to mean a group derived from
an aliphatic hydrocarbon having at least one heteroatom and having
two or more points of attachment. The term "alkenyl" is intended to
mean a group derived from a hydrocarbon having one or more
carbon-carbon double bonds and having one point of attachment,
which group may be unsubstituted or substituted. The term "alkynyl"
is intended to mean a group derived from a hydrocarbon having one
or more carbon-carbon triple bonds and having one point of
attachment, which group may be unsubstituted or substituted. The
term "alkenylene" is intended to mean a group derived from a
hydrocarbon having one or more carbon-carbon double bonds and
having two or more points of attachment, which group may be
unsubstituted or substituted. The term "alkynylene" is intended to
mean a group derived from a hydrocarbon having one or more
carbon-carbon triple bonds and having two or more points of
attachment, which group may be unsubstituted or substituted. The
terms "heteroalkenyl", "heteroalkenylene", "heteroalkynyl" and
"heteroalkynlene" are intended to mean analogous groups having one
or more heteroatoms. The term "alkenylene" is intended to mean a
group derived from a hydrocarbon having one or more carbon-carbon
double bonds and having two or more points of attachment, which
group may be unsubstituted or substituted. The term "alkynylene" is
intended to mean a group derived from a hydrocarbon having one or
more carbon-carbon triple bonds and having two or more points of
attachment, which group may be unsubstituted or substituted. The
terms "heteroalkenyl", "heteroalkenylene", "heteroalkynyl" and
"heteroalkynlene" are intended to mean analoguse groups having one
or more heteroatoms. The term "aryl" is intended to mean a group
derived from an aromatic hydrocarbon having one point of
attachment, which group may be unsubstituted or substituted. The
term "heteroaryl" is intended to mean a group derived from an
aromatic group having at least one heteroatom and having one point
of attachment, which group may be unsubstituted or substituted. The
term "arylalkylene" is intended to mean a group derived from an
alkyl group having an aryl substituent, which group may be further
unsubstituted or substituted. The term "heteroarylalkylene" is
intended to mean a group derived from an alkyl group having a
heteroaryl substituent, which group may be further unsubstituted or
substituted. The term "arylene" is intended to mean a group derived
from an aromatic hydrocarbon having two points of attachment, which
group may be unsubstituted or substituted. The term "heteroarylene"
is intended to mean a group derived from an aromatic group having
at least one heteroatom and having two points of attachment, which
group may be unsubstituted or substituted. The term
"arylenealkylene" is intended to mean a group having both aryl and
alkyl groups and having one point of attachment on an aryl group
and one point of attachment on an alkyl group. The term
"heteroarylenealkylene" is intended to mean a group having both
aryl and alkyl groups and having one point of attachment on an aryl
group and one point of attachment on an alkyl group, and in which
there is at least one heteroatom. Unless otherwise indicated, all
groups can be unsubstituted or substituted. The phrase "adjacent
to," when used to refer to layers in a device, does not necessarily
mean that one layer is immediately next to another layer. On the
other hand, the phrase "adjacent R groups," is used to refer to R
groups that are next to each other in a chemical formula (i.e., R
groups that are on atoms joined by a bond). The term "compound" is
intended to mean an electrically uncharged substance made up of
molecules that further consist of atoms, wherein the atoms cannot
be separated by physical means. The term "ligand" is intended to
mean a molecule, ion, or atom that is attached to the coordination
sphere of a metallic ion. The term "complex", when used as a noun,
is intended to mean a compound having at least one metallic ion and
at least one ligand. The term "polymeric" is intended to encompass
oligomeric species and include materials having 2 or more monomeric
units. In addition, the IUPAC numbering system is used throughout,
where the groups from the Periodic Table are numbered from left to
right as 1 through 18 (CRC Handbook of Chemistry and Physics,
81.sup.st Edition, 2000).
[0024] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. Unless
otherwise defined, all letter symbols in the figures represent
atoms with that atomic abbreviation. Although methods and materials
similar or equivalent to those described herein can be used in the
practice or testing of the present invention, suitable methods and
materials are described below. All publications, patent
applications, patents, and other references mentioned herein are
incorporated by reference in their entirety. In case of conflict,
the present specification, including definitions, will control. In
addition, the materials, methods, and examples are illustrative
only and not intended to be limiting.
[0025] Other features and advantages of the invention will be
apparent from the following detailed description, and from the
claims.
DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 shows Formula I for a charge transport composition of
the invention.
[0027] FIG. 2 shows Formula II for a charge transport composition
of the invention.
[0028] FIG. 3 shows Formulae I(a) through I(s) for a charge
transport composition of the invention.
[0029] FIG. 4 shows Formulae III(a) through III(h) for a
multidentate linking group.
[0030] FIG. 5 shows Formulae II(a) through II(f) for a charge
transport composition of the invention.
[0031] FIG. 6 shows Formulae IV(a) through IV(e) for
electroluminescent iridium complexes.
[0032] FIG. 7 is a schematic diagram of a light-emitting diode
(LED).
[0033] FIG. 8 is shows formulae for known hole transport
materials.
[0034] FIG. 9 is a schematic diagram of a testing device for an
LED.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] The triarylmethane compounds represented by Formula I, shown
in FIG. 1, have particular utility as hole transport compositions.
The compound
bis(4-N,N-diethylamino-2-methylphenyl)-4-methylphenylmethane (MPMP)
has been disclosed to be a suitable hole transport composition in
Petrov et al., Published PCT application WO 02/02714. Other
triarylmethane derivatives have not been used in OLED devices.
[0036] In general, n is an integer. In one embodiment, n is an
integer from 1 through 20. In one embodiment, n is an integer from
1 through 12.
[0037] In one embodiment, Ar.sup.1 is selected from phenyl and
biphenyl groups, which may have one or more carbon atoms replaced
with a heteroatom. All of these groups may further be substituted.
Examples of substituents include, but are not limited to, alkyl,
heteroalkyl, aryl, heteroaryl, arylalkylene, heteroarylalkylene,
C.sub.nH.sub.aF.sub.b, and C.sub.6H.sub.cF.sub.d, where a through d
and n are as defined above.
[0038] In one embodiment, the Ar.sup.1 in the X.sub.5Ar.sup.1 group
is selected from phenyl, biphenyl, pyridyl, and bipyridyl, which
may further be substituted. Examples of substituents include, but
are not limited to, alkyl, heteroalkyl, aryl, heteroaryl,
arylalkylene, heteroarylalkylene, C.sub.nH.sub.aF.sub.b, and
C.sub.6H.sub.cF.sub.d, where a through d and n are as defined
above.
[0039] In one embodiment, X is a fused heteroaromatic ring group.
Examples of such groups include, but are not limited to,
N-carbazoles, benzodiazoles, and benzotriazoles.
[0040] In one embodiment, N(R.sup.1).sub.2 is a fused
heteroaromatic ring group. Examples of such groups include, but are
not limited to, carbazoles, benzodiazoles, and benzotriazoles.
[0041] In one embodiment R.sup.1 is selected from alkyl groups
having 1 through 12 carbon atoms, phenyl and benzyl.
[0042] In one embodiment, there is at least one substituent on an
aryl ring selected from F, C.sub.nH.sub.aF.sub.b,
OC.sub.nH.sub.aF.sub.b, C.sub.6H.sub.cF.sub.d, and
OC.sub.6H.sub.cF.sub.d, where a through d and n are as defined
above.
[0043] In one embodiment, there is at least one X group selected
from F, C.sub.nH.sub.aF.sub.b, OC.sub.nH.sub.aF.sub.b,
C.sub.6H.sub.cF.sub.d, and OC.sub.6H.sub.cF.sub.d, where a through
d and n are as defined above.
[0044] Examples of suitable hole transport compounds of the
invention include, but are not limited to, those given as Formulae
I(a) through I(t), shown in FIG. 3.
[0045] The compositions represented by Formula I can be prepared
using standard synthetic organic techniques, as illustrated in the
examples. The compounds can be applied as thin films by evaporative
techniques or conventional solution processing methods. As used
herein, "solution processing" refers to the formation of films from
a liquid medium. The liquid medium can be in the form of a
solution, a dispersion, an emulsion, or other forms. Typical
solution processing techniques include, for example, solution
casting, drop casting, curtain casting, spin-coating, screen
printing, inkjet printing, gravure printing, and the like.
[0046] In some cases it is desirable to increase the Tg of the
compounds to improve stability, coatability, and other properties.
This can be accomplished by linking together two or more of the
compounds with a linking group to form compounds having Formula II,
shown in FIG. 2. In Formula II, the carbon atom shown as "C" is
referred to as a "triarylmethane carbon". In this formula, Q can be
a single bond or a multivalent linking group, having two or more
points of attachment. The multivalent linking group can be a
hydrocarbon group with two or more points of attachment, and can be
aliphatic or aromatic. The multivalent linking group can be a
heteroalkyl or heteroaromatic group, where the heteroatoms can be,
for example, N, O, S, or Si. Examples of multivalent groups, Q,
include, but are not limited to, alkylene, alkenylene, and
alkynylene groups, and analogous compounds with heteroatoms;
single, multiple-ring, and fused-ring aromatics and
heteroaromatics; arylamines, such as triarylamines; silanes and
siloxanes. Additional examples of multivalent Q groups are given in
FIG. 4 as Formulae III(a) through III(h). In Formula III(f), any of
the carbons may be linked to a charge transport moiety. In Formula
III(h), any of the Si atoms can be linked to a charge transport
moiety. Heteroatoms such as Ge and Sn can also be used. The linking
group can also be --[SiMeR.sup.1--SiMeR.sup.1].sub.n--, where
R.sup.1 and n are as defined above.
[0047] In general, m is an integer equal to at least 2. The exact
number depends on the number of available linking positions on Q
and on the geometries of the triarylmethane moiety and Q. In one
embodiment, m is an integer from 2 through 10.
[0048] In general, n is an integer. In one embodiment, n is an
integer from 1 through 20. In one embodiment, n is an integer from
1 through 12.
[0049] In one embodiment, Ar.sup.1 is selected from phenyl and
biphenyl groups, which may have one or more carbon atoms replaced
with a heteroatom. All of these groups may further be substituted.
Examples of substituents include, but are not limited to, alkyl,
heteroalkyl, aryl, heteroaryl, arylalkylene, heteroarylalkylene,
C.sub.nH.sub.aF.sub.b, and C.sub.6H.sub.cF.sub.d, where a through d
and n are as defined above.
[0050] In one embodiment, N(R.sup.1).sub.2 is a fused
heteroaromatic ring group. Examples of such groups include, but are
not limited to, carbazoles, benzodiazoles, and benzotriazoles.
[0051] In one embodiment R.sup.1 is selected from alkyl groups
having 1 through 12 carbon atoms, phenyl and benzyl.
[0052] In one embodiment, R.sup.2 is selected from phenyl,
biphenyl, pyridyl, and bipyridyl, which may further be substituted.
Examples of substituents include, but are not limited to, alkyl,
heteroalkyl, aryl, heteroaryl, arylalkylene, heteroarylalkylene,
C.sub.nH.sub.aF.sub.b, and C.sub.6H.sub.cF.sub.d, where a through d
and n are as defined above.
[0053] In one embodiment, at least one R.sup.1 is selected from F,
C.sub.nH.sub.aF.sub.b, OC.sub.nH.sub.aF.sub.b,
C.sub.6H.sub.cF.sub.d, and OC.sub.6H.sub.cF.sub.d, where a through
d and n are as defined above.
[0054] The compositions represented by Formula II can be prepared
using standard synthetic organic techniques, as illustrated in the
examples. The compounds can be applied as thin films by evaporative
techniques or conventional solution processing methods. As used
herein, "solution processing" refers to the formation of films from
a liquid medium. The liquid medium can be in the form of a
solution, a dispersion, an emulsion, or other forms. Typical
solution processing techniques include, for example, solution
casting, drop casting, curtain casting, spin-coating, screen
printing, inkjet printing, gravure printing, and the like.
[0055] Examples of linked compounds having Formula II include, but
are not limited to, those given in FIG. 5, Formulae II(a) through
II(h).
Electronic Device
[0056] The present invention also relates to an electronic device
comprising at least one of the charge transport compositions of the
invention. The charge transport compositions can be in a separate
layer, positioned between a photoactive layer and one electrode.
Alternatively, the charge transport compositions of the invention
can be in the photoactive layer. A typical device structure is
shown in FIG. 7. The device 100 has an anode layer 110 and a
cathode layer 160. Adjacent to the anode is a layer 120 comprising
hole transport material. Adjacent to the cathode is a layer 140
comprising an electron transport and/or anti-quenching material.
Between the hole transport layer and the electron transport and/or
anti-quenching layer is the photoactive layer 130. As an option,
devices frequently use another electron transport layer 150, next
to the cathode. Layers 120, 130, 140, and 150 are individually and
collectively referred to as the active layers.
[0057] Depending upon the application of the device 100, the
photoactive layer 130 can be a light-emitting layer that is
activated by an applied voltage (such as in a light-emitting diode
or light-emitting electrochemical cell), a layer of material that
responds to radiant energy and generates a signal with or without
an applied bias voltage (such as in a photodetector). Examples of
photodetectors include photoconductive cells, photoresistors,
photoswitches, phototransistors, and phototubes, and photovoltaic
cells, as these terms are describe in Markus, John, Electronics and
Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).
[0058] The triarylmethane derivative compounds of the invention are
particularly useful as the hole transport layer 120, and as a
charge conducting host in the photoactive layer, 130. The other
layers in the device can be made of any materials which are known
to be useful in such layers. The anode 110, is an electrode that is
particularly efficient for injecting positive charge carriers. It
can be made of, for example materials containing a metal, mixed
metal, alloy, metal oxide or mixed-metal oxide, or it can be a
conducting polymer, and mixtures thereof. Suitable metals include
the Group 11 metals, the metals in Groups 4, 5, and 6, and the
Group 8-10 transition metals. If the anode is to be
light-transmitting, mixed-metal oxides of Groups 12, 13 and 14
metals, such as indium-tin-oxide, are generally used. The anode 110
may also comprise an organic material such as polyaniline as
described in "Flexible light-emitting diodes made from soluble
conducting polymer," Nature vol. 357, pp 477-479 (11 Jun. 1992). At
least one of the anode and cathode should be at least partially
transparent to allow the generated light to be observed.
[0059] Examples of the photoactive layer 130 include all known
electroluminescent materials. Organometallic electroluminescent
compounds are preferred. The most preferred compounds include
cyclometalated iridium and platinum electroluminescent compounds
and mixtures thereof. Complexes of Iridium with phenylpyridine,
phenylquinoline, or phenylpyrimidine ligands have been disclosed as
electroluminescent compounds in Petrov et al., Published PCT
Application WO 02/02714. Other organometallic complexes have been
described in, for example, published applications US 2001/0019782,
EP 1191612, WO 02/15645, and EP 1191614. Electroluminescent devices
with an active layer of polyvinyl carbazole (PVK) doped with
metallic complexes of iridium have been described by Burrows and
Thompson in published PCT applications WO 00/70655 and WO 01/41512.
Electroluminescent emissive layers comprising a charge carrying
host material and a phosphorescent platinum complex have been
described by Thompson et al., in U.S. Pat. No. 6,303,238, Bradley
et al., in Synth. Met. (2001), 116 (1-3), 379-383, and Campbell et
al., in Phys. Rev. B, Vol. 65 085210. Examples of a few suitable
iridium complexes are given in FIG. 6, as Formulae IV(a) through
IV(e). Analogous tetradentate platinum complexes can also be used.
These electroluminescent complexes can be used alone, or doped into
charge-carrying hosts, as noted above. The molecules of the present
invention, in addition to being useful in the hole transport layer
120, may also act as a charge carrying host for the emissive dopant
in the photoactive layer 130.
[0060] Examples of electron transport materials which can be used
in layer 140 and/or layer 150 include metal chelated oxinoid
compounds, such as tris(8-hydroxyquinolato)aluminum (Alq.sub.3);
and azole compounds such as
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and
3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ),
and mixtures thereof.
[0061] The cathode 160, is an electrode that is particularly
efficient for injecting electrons or negative charge carriers. The
cathode can be any metal or nonmetal having a lower work function
than the anode. Materials for the cathode can be selected from
alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline
earth) metals, the Group 12 metals, including the rare earth
elements and lanthanides, and the actinides. Materials such as
aluminum, indium, calcium, barium, samarium and magnesium, as well
as combinations, can be used. Li-containing organometallic
compounds, LiF, and Li.sub.2O can also be deposited between the
organic layer and the cathode layer to lower the operating
voltage.
[0062] It is known to have other layers in organic electronic
devices. For example, there can be a layer (not shown) between the
anode 110 and hole transport layer 120 to facilitate positive
charge transport and/or band-gap matching of the layers, or to
function as a protective layer. Layers that are known in the art
can be used. In addition, any of the above-described layers can be
made of two or more layers. Alternatively, some or all of anode
layer 110, the hole transport layer 120, the electron transport
layers 140 and 150, and cathode layer 160, may be surface treated
to increase charge carrier transport efficiency. The choice of
materials for each of the component layers is preferably determined
by balancing the goals of providing a device with high device
efficiency with device operational lifetime.
[0063] It is understood that each functional layer may be made up
of more than one layer.
[0064] The device can be prepared by a variety of techniques,
including sequentially vapor depositing the individual layers on a
suitable substrate. Substrates such as glass and polymeric films
can be used. Conventional vapor deposition techniques can be used,
such as thermal evaporation, chemical vapor deposition, and the
like. Alternatively, the organic layers can be applied from
solutions or dispersions in suitable solvents, using any
conventional coating or printing technique, including but not
limited to spin-coating, dip-coating, roll-to-roll techniques,
ink-jet printing, screen-printing, gravure printing and the like.
In general, the different layers will have the following range of
thicknesses: anode 110, 500-5000 .ANG., preferably 1000-2000 .ANG.;
hole transport layer 120, 50-2000 .ANG., preferably 200-1000 .ANG.;
photoactive layer 130, 10-2000 .ANG., preferably 100-1000 .ANG.;
electron transport layer 140 and 150, 50-2000 .ANG., preferably
100-1000 .ANG.; cathode 160, 200-10000 .ANG., preferably 300-5000
.ANG.. The location of the electron-hole recombination zone in the
device, and thus the emission spectrum of the device, can be
affected by the relative thickness of each layer. Thus the
thickness of the electron-transport layer should be chosen so that
the electron-hole recombination zone is in the light-emitting
layer. The desired ratio of layer thicknesses will depend on the
exact nature of the materials used.
[0065] The triarylmethane derivative compounds of the invention may
be useful in applications other than OLEDs. For example, these
compositions may be used in photovoltaic devices for solar energy
conversion. They may also be used in field effect transistor for
smart card and thin film transistor (TFT) display driver
applications.
EXAMPLES
[0066] The following examples illustrate certain features and
advantages of the present invention. They are intended to be
illustrative of the invention, but not limiting. All percentages
are by weight, unless otherwise indicated.
Example 1
[0067] This example illustrates the preparation of triarylmethane
hole transport compositions, shown in FIG. 3.
Compound I(f): 32.6 g of N,N-diethyl-m-toluidine and 12.4 g
p-fluorobenzaldehyde were mixed in 30 mL ethanol and 10 mL conc.
HCl. This mixture was gently refluxed under nitrogen for 16 hrs at
which point the mixture was cooled and poured into 250 mL distilled
water. The solution was adjusted to pH 8 with sodium hydroxide (1M)
solution and the ethanol removed by rotovap. The aqueous layer was
decanted from the solid residue which was then washed with 100 mL
distilled water and finally recrystallized from hot ethanol. The
crystalline white solid was dried in vacuo and then tested for OLED
device utility. Yield 46%; 1H nmr (CDCl3): 6.9 (m); 6.82 (t); 6.45
(m); 6.35 (m); 5.38 (s); 3.23 (q); 2.02 (s); 1.05 (t). 19F nmr:
-118.6 (s); MPt 100 C
[0068] Other triarylmethane compounds were made similarly
substituting on equivalent of the appropriate aldehyde for
p-fluorobenzaldehyde in the above procedure.
Compound I(a): Yield 58%; MPt 113 C; 1H nmr: 7.1 (t); 7.0 (t); 6.9
(d); 6.4 (d); 6.35 (s); 6.28 (d); 5.37 (s); 3.15 (q); 1.97 (s); 1.0
(t)
Compound I(b): Yield 64%; MPt 167.degree. C.; 1H nmr: 7.45 (d); 7.1
(d); 6.4 (m); 6.35 (m); 5.45 (s); 3.23 (q); 2.02 (s); 1.05 (t)
Compound I(c): Yield 79%; MPt 161.degree. C.; 1H nmr: 8.10 (d);
7.16 (d); 6.4 (m); 6.35 (m); 5.50 (s); 3.23 (q); 2.02 (s); 1.05
(t)
Compound I(d): Yield 62%; MPt 143.degree. C.; 1H nmr: 7.38 (d);
6.97 (d); 6.54 (m); 6.42 (m); 5.47 (s); 3.35 (q); 2.12 (s); 1.15
(t)
Compound I(e): Yield 48%; MPt 96.degree. C.; 1H nmr: 6.88 (d); 6.71
(d); 6.5 (d); 6.41 (m); 6.3 (m); 5.35 (s); 3.23 (q); 2.02 (s); 1.05
(t)
Compound I(g): Yield 3%; MPt. 155.degree. C.; 1H nmr: 6.95 (d);
6.72 (d); 6.62 (d); 6.55 (m); 6.45 (m); 5.45 (s); 4.64 (s); 3.33
(q); 2.12 (s); 1.15 (t)
Compound I(h): Yield 14%; MPt. 139.degree. C.; 1H nmr: 6.80 (d);
6.6 (d); 6.5 (m); 6.38 (m); 5.33 (s); 2.80 (s); 2.06 (s)
Compound I(i): Yield 40%; MPt. 163.degree. C.; 1H nmr: 7.16 (d);
6.87 (d); 6.51 (d); 6.40 (s); 6.32 (d); 5.38 (s); 3.23 (q); 2.02
(s); 1.21 (s); 1.05 (t)
Compound I(j): Yield 59%; MPt. 159.degree. C.; 1H nmr: 7.51 (d);
7.38 (d); 7.33 (t); 7.22 (t) 7.05 (d) 6.54 (d); 6.43 (s); 6.35 (d);
5.45 (s); 3.23 (q); 2.02 (s); 1.05 (t)
Compound I(k): Yield 7%; MPt. 198.degree. C.; 1H nmr: 6.70 (d);
6.42 (m); 5.68 (s); 3.23 (q); 2.02 (s); 1.05 (t); 19F nmr: -140.6
(m); -158.0 (m); -163.0 (m)
Compound I(l): Yield 98%; MPt. 122 C; 1H nmr: 7.18 (d); 7.13 (s);
7.00 (t); 6.85 (d); 6.42 (d); 6.39 (s); 6.30 (m); 5.35 (s); 3.23
(q); 2.02 (s); 1.05 (t)
Compound I(m): Yield 68%; MPt. 147 C; 1H nmr: 7.30 (d); 6.96 (d);
6.32 (m); 6.24 (m); 5.34 (s); 3.13 (q); 1.95 (s); 1.00 (t); 19F
nmr: -62.6 (s)
Compound I(n): Yield 57%; MPt. 150 C; 1H nmr: 7.20 (m); 6.88 (m);
6.4 (m); 6.35 (m); 5.38 (s); 3.23 (q); 2.02 (s); 1.05 (t); 19F nmr:
-112.6 (s)
Compound I(o): Yield 41%; MPt. 135 C; 1H nmr: 8.58 (d); 7.79 (d);
7.6 (m); 7.1 (d); 6.54 (d); 6.42 (s); 6.35 (d); 5.47 (s); 3.23 (q);
2.02 (s); 1.05 (t)
Compound I(p): Yield 43%; MPt. 111 C; 1H nmr: 7.50 (s); 6.4 (m);
6.35 (m); 5.50 (s); 3.23 (q); 2.02 (s); 1.05 (t); 19F nmr: -108.1
(s); -108.5 (s).
Example 2
[0069] This examples illustrates the preparation of a hole
transport compound having multiple triarylmethane groups, Compound
II(c) in FIG. 5.
Step 1:
[0070] 1,3,5,7-Tetraphenyl adamantane was prepared according to:
Newman, H., Synthesis 1972, 692.
[0071] In a dry box: to a 100-mL, jacketed, one-neck, round-bottom
flask equipped with a magnetic stirring bar and NaOH drying tube,
was added 1,3,5,7-tetraphenyladamantane (1.00 g, 2.27 mmol) and 30
mL anhydrous methylene chloride. The undissolved reaction mixture
was cooled to -5.degree. C. and then charged with TiCl.sub.4 (3.38
mL, 30.82 mmol) and then dichloromethylmethylether (3.38 mL, 37.37
mL). The reaction stirred 17 h. at -5.degree. C. and was then
poured into crushed ice. The aqueous layer was diluted to 300 mL,
vigorously shaken and the layers then separated. The organic layer
was then washed with 200-mL brine, dried over MgSO.sub.4 and then
concentrated to afford a yellow solid. The crude material was
dissolved in hot ethyl acetate, and then diluted with hexane until
the formation of a precipitate was observed. The mixture was
filtered, the precipitate discarded, and the filtrate concentrated
by rotary evaporation, affording 0.5520 g of a white waxy
solid.
Step 2:
[0072] A 100-mL, one-neck, round-bottom flask, equipped with
magnetic stirring bar, Dean-Stark trap, condenser, and nitrogen
inlet was charged with 1,3,5,7-adamantane tetrakisbenzaldehyde
(0.55 g, 1.0 mmol), 60 mL n-butanol, 20 mL conc. HCl, and
N,N-diethyl-m-toluamide (0.666 g, 4.08 mmol). The reaction mixture
was heated at reflux for 24 h. and then water was azeotropically
distilled over an additional 16 h. The remaining green solution was
concentrated by rotary evaporation, dissolved in 150 mL methylene
chloride and washed with 150 mL water. The aqueous layer was
adjusted to pH 8 by addition of a saturated solution of sodium
bicarbonate. The mixture was shaken, the layers separated, the
organic layer dried over MgSO.sub.4, and then concentrated by
rotary evaporation affording 1.4958 g of a brown glassy solid.
Purification by flash chromatography over silica gel (2.5% i-PrOH
in CH.sub.2Cl.sub.2) afforded 0.8977 g of a tan glassy solid.
Example 3
[0073] This example illustrates the preparation of an iridium
electroluminescent complex, shown as Formula IV(a) in FIG. 6.
Phenylpyridine Ligand,
2-(4-fluorophenyl)-5-trifluoromethylpyridine
[0074] The general procedure used was described in O. Lohse, P.
Thevenin, E. Waldvogel Synlett, 1999, 45-48. A mixture of 200 ml of
degassed water, 20 g of potassium carbonate, 150 ml of
1,2-dimethoxyethane, 0.5 g of Pd(PPh.sub.3).sub.4, 0.05 mol of
2-chloro-5-trifluoromethylpyridine and 0.05 mol of
4-fluorophenylboronic acid was refluxed (80-90.degree. C.) for
16-30 h. The resulting reaction mixture was diluted with 300 ml of
water and extracted with CH.sub.2Cl.sub.2 (2.times.100 ml). The
combined organic layers were dried over MgSO.sub.4, and the solvent
removed by vacuum. The liquid products were purified by fractional
vacuum distillation. The solid materials were recrystallized from
hexane. The typical purity of isolated materials was >98%.
Iridium Complex:
[0075] A mixture of IrCl.sub.3.nH.sub.2O (54% Ir; 508 mg),
2-(4-fluorophenyl)-5-trifluoromethylpyridine, from above (2.20 g),
AgOCOCF.sub.3 (1.01 g), and water (1 mL) was vigorously stirred
under a flow of N.sub.2 as the temperature was slowly (30 min)
brought up to 185.degree. C. (oil bath). After 2 hours at
185-190.degree. C. the mixture solidified. The mixture was cooled
down to room temperature. The solids were extracted with
dichloromethane until the extracts decolorized. The combined
dichloromethane solutions were filtered through a short silica
column and evaporated. After methanol (50 mL) was added to the
residue the flask was kept at -10.degree. C. overnight. The yellow
precipitate of the tris-cyclometalated complex, compound IVa, was
separated, washed with methanol, and dried under vacuum. Yield:
1.07 g (82%). X-Ray quality crystals of the complex were obtained
by slowly cooling its warm solution in 1,2-dichloroethane.
Example 4
[0076] This example illustrates the formation of OLEDs using the
charge transport compositions of the invention.
[0077] Thin film OLED devices including a hole transport layer (HT
layer), electroluminescent layer (EL layer) and at least one
electron transport and/or anti-quenching layer (ET/AQ layer) were
fabricated by the thermal evaporation technique. An Edward Auto 306
evaporator with oil diffusion pump was used. The base vacuum for
all of the thin film deposition was in the range of 10.sup.-6 torr.
The deposition chamber was capable of depositing five different
films without the need to break up the vacuum.
[0078] Patterned indium tin oxide (ITO) coated glass substrates
from Thin Film Devices, Inc was used. These ITO's are based on
Corning 1737 glass coated with 1400 .ANG. ITO coating, with sheet
resistance of 30 ohms/square and 80% light transmission. The
patterned ITO substrates were then cleaned ultrasonically in
aqueous detergent solution. The substrates were then rinsed with
distilled water, followed by isopropanol, and then degreased in
toluene vapor for .about.3 hours.
[0079] The cleaned, patterned ITO substrate was then loaded into
the vacuum chamber and the chamber was pumped down to 10.sup.-6
torr. The substrate was then further cleaned using an oxygen plasma
for about 5-10 minutes. After cleaning, multiple layers of thin
films were then deposited sequentially onto the substrate by
thermal evaporation. Finally, patterned metal electrodes of Al or
LiF and Al were deposited through a mask. The thickness of the film
was measured during deposition using a quartz crystal monitor
(Sycon STC-200). All film thickness reported in the Examples are
nominal, calculated assuming the density of the material deposited
to be one. The completed OLED device was then taken out of the
vacuum chamber and characterized immediately without
encapsulation.
[0080] Table 1 summarizes the devices made with the hole transport
compositions of the invention, and with the comparative hole
transport compounds shown in FIG. 8. In all cases emitting layer
was the iridium complex from Example 3, having the thickness
indicated. The electron transport layer 140 was
4,7-diphenyl-1,10-phenanthroline, DPA. When present, electron
transport layer 150 was tris(8-hydroxyquinolato)aluminum(III), Alq,
each having the thicknesses given. The cathode was a layer of Al or
a dual layer of LiF/Al, with the thicknesses given.
TABLE-US-00001 TABLE 1 Devices HT Sample (.ANG.) EL, .ANG. ET/AQ,
.ANG. ET, .ANG. Cathode, .ANG. Comparative A Comp. A 405 DPA 103
Alq 305 LiF 10 509 Al 512 Comparative B Comp. B 403 DPA 411 Al 735
510 Comparative C Comp. C 433 DPA 414 Al 734 506 Comparative D
Comp. D 412 DPA 417 Al 726 505 Comparative E Comp. E 404 DPA 101
Alq 304 LiF 10 302 Al 453 1-1 I(a) 402 DPA 101 Alq 302 LiF 10 302
Al 453 1-2 I(b) 403 DPA 103 Alq 304 LiF 10 303 Al 452 1-3 I(c) 403
DPA 101 Alq 303 LiF 10 303 Al 454 1-4 I(d) 405 DPA 101 Alq 303 LiF
10 303 Al 454 1-5 I(e) 404 DPA 101 Alq 303 LiF 10 303 Al 453 1-6
I(f) 404 DPA 102 Alq 302 LiF 10 303 Al 452 1-7 I(g) 405 DPA 103 Alq
302 LiF 10 304 Al 452 1-8 I(h) 403 DPA 102 Alq 302 LiF 10 302 Al
453 1-9 I(i) 404 DPA 105 Alq 302 LiF 10 305 Al 453 1-10 I(j) 403
DPA 102 Alq 303 LiF 10 305 Al 453 1-11 I(k) 403 DPA 101 Alq 303 LiF
10 304 Al 317 1-12 I(l) 403 DPA 100 Alq 302 LiF 10 301 Al 330 1-13
I(m) 405 DPA 102 Alq 305 LiF 10 302 Al 453 1-14 I(n) 403 DPA 102
Alq 303 LiF 10 302 Al 451 1-15 II(a) 404 DPA 102 Alq 304 LiF 10 302
Al 452 1-16 II(b) 402 DPA 101 Alq 301 LiF 10 302 Al 454
[0081] The OLED samples were characterized by measuring their (1)
current-voltage (I-V) curves, (2) electroluminescence radiance
versus voltage, and (3) electroluminescence spectra versus voltage.
The apparatus used, 200, is shown in FIG. 9. The I-V curves of an
OLED sample, 220, were measured with a Keithley Source-Measurement
Unit Model 237, 280. The electroluminescence radiance (in the unit
of cd/m.sup.2) vs. voltage was measured with a Minolta LS-110
luminescence meter, 210, while the voltage was scanned using the
Keithley SMU. The electroluminescence spectrum was obtained by
collecting light using a pair of lenses, 230, through an electronic
shutter, 240, dispersed through a spectrograph, 250, and then
measured with a diode array detector, 260. All three measurements
were performed at the same time and controlled by a computer, 270.
The efficiency of the device at certain voltage is determined by
dividing the electroluminescence radiance of the LED by the current
density needed to run the device. The unit is in cd/A.
[0082] The results for devices using the triarylmethane hole
transport compositions of the invention are given in Table 2
below:
TABLE-US-00002 TABLE 2 Electroluminescent Properties of Devices
Peak Peak Radiance, efficiency, Sample cd/m2 cd/A Comp. A 7000 at
14 V 24 Comp. B 3700 at 21 V 16 Comp. C 500 at 17 V 1.1 Comp. D
1500 at 16 V 1.5 Comp. E 18000 at 11 V 12 at 9 V; 8 lm/W at 5 V 1-1
6000 at 15 V 22 1-2 6000-7400 at 17 V 14-17 1-3 40 at 23 V .25 1-4
700 at 13 V 6-10 1-5 7000 at 15 V 20 1-6 11000 at 13 V 35 1-7 3700
at 15 V 10 1-8 2600 at 15 V 11.5 1-9 4000 at 16 V 20 at 11 V 1-10
3400 at 16 V 5 at 12 V 1-11 800 at 14 V 10 at 13 V 1-12 110 at 12 V
20 at 10 V 1-13 450 at 10 V 8 at 10 V 1-14 250 at 9 V 9 at 10 V
1-15 1500-2000 at 18 V 6.5 at 14 V 1-16 1000-1500 at 18 V 5.5 at 12
V
Example 5
[0083] This example illustrates the preparation of Compound I(q) in
FIG. 3.
[0084] 1.2 g tolualdehyde and 5.8 g m-dibenzylamino-toluene were
mixed in 3 mL ethanol and 1 mL concentrated HCl. The mixture was
then gently refluxed under nitrogen for 2 days. The resulting
material was poured into 25 mL water and the pH was adjusted to 8
with sodium hydroxide solution (1N). The ethanol solvent was
rotovaporated and the aqueous supernatant was decanted from the
greenish organic layer. The organic layer was triturated with dry
ethanol until it became a greenish solid. After recrystallization
from boiling ethanol, the material was rapidly chromatographed on
neutral alumina using methylene chloride eluent to remove colored
impurities and aldehyde contaminants. The resulting white solid was
collected and dried in vacuum. Yield 1.0 g .about.15%.
Example 6
[0085] This example illustrates the preparation of Compound II(d)
in FIG. 5.
[0086] 12.5 g iso-phthalaldehyde and 59.0 g m-diethylamino-toluene
were mixed in 55 mL ethanol and 18 mL concentrated HCl. The mixture
was then gently refluxed under nitrogen for 60 hrs. The resulting
material was poured into 100 mL water and the pH was adjusted to 8
with sodium hydroxide solution (1N). The ethanol solvent was
rotovaporated and the aqueous supernatant was decanted from the
greenish organic layer. The organic layer was washed with 100 mL
distilled water and then triturated with dry ethanol until it
became a greenish solid. After recrystallization from boiling
ethanol, the material was rapidly chromatographed on neutral
alumina using methylene chloride eluent to remove colored
impurities and aldehyde contaminants. The resulting white solid was
collected and dried in vacuum. Yield 25.5 g .about.39%.
Example 7
[0087] This example illustrates the preparation of Compound I(r) in
FIG. 3.
[0088] 14.0 g diphenylamino-p-benzaldehyde and 16.3 g
m-diethylamino-toluene were mixed in 15 mL ethanol and 5 mL
concentrated HCl. The mixture was then gently refluxed under
nitrogen for 48 hrs. The resulting material was poured into 25 mL
water and the pH was adjusted to 8 with sodium hydroxide solution
(1N). The ethanol solvent was rotovaporated and the aqueous
supernatant was decanted from the bluish organic layer. The organic
layer was washed with 100 mL distilled water and then triturated
with dry ethanol until it became a tan colored solid. After
recrystallization from boiling ethanol, the material was rapidly
chromatographed on neutral alumina using methylene chloride eluent
to remove colored impurities and aldehyde contaminants. The
resulting white solid was collected and dried in vacuum. Yield 9.0
g .about.31%.
Example 8
[0089] This example illustrates the preparation of Compound I(s) in
FIG. 3.
[0090] 5.0 g 3-vinylbenzaldehyde and 11.0 g m-diethylamino-toluene
were mixed in 10 mL ethanol and 3.4 mL concentrated HCl. The
mixture was then gently refluxed under nitrogen for 48 hrs. The
resulting material was poured into 25 mL water and the pH was
adjusted to 8 with sodium hydroxide solution (1N). The ethanol
solvent was rotovaporated and the aqueous supernatant was decanted
from the greenish organic layer. The organic layer was washed with
100 mL distilled water and then triturated with dry ethanol until
it became a tan colored solid. After recrystallization from boiling
ethanol, the material was rapidly chromatographed on neutral
alumina using methylene chloride eluent to remove colored
impurities and aldehyde contaminants. The resulting white solid was
collected and dried in vacuum. Yield 4.5 g .about.34%.
Example 9
[0091] This example illustrates the preparation of Compound II(e)
in FIG. 5.
[0092] 2.64 g 3,5-dibromobenzaldehyde, 3.0 g 4-formylboronic acid,
0.4 g tetrakistriphenylphosphine palladium, 3.2 g potassium
carbonate, 40 mL water and 40 mL dimethoxyethane was combined under
nitrogen and refluxed for 20 hrs. After cooling to room temperature
the organic layer was collected and the aqueous layer was extracted
3.times. with 25 mL portions of methylene chloride. All extracts
and organic layer were combined and dried over magnesium sulfate
before filtering and evaporating to dryness. The resultant product
trialdehyde was isolated and characterized by nmr in yield of 2.6 g
.about.84%.
[0093] The trialdehyde material 2.6 g was combined with 8.1 g
m-diethylamino-toluene and mixed in 7.5 mL ethanol and 2.5 mL
concentrated HCl. The mixture was then gently refluxed under
nitrogen for 48 hrs. The resulting material was poured into 25 mL
water and the pH was adjusted to 8 with sodium hydroxide solution
(1N). The ethanol solvent was rotovaporated and the aqueous
supernatant was decanted from the olive green organic layer. The
organic layer was washed with 100 mL distilled water and then
triturated with dry ethanol until it became a tan colored solid.
After recrystallization from boiling ethanol, the material was
rapidly chromatographed on neutral alumina using methylene chloride
eluent to remove colored impurities and aldehyde contaminants. The
resulting white solid was collected and dried in vacuum. Yield 1.2
g .about.15%.
Example 10
[0094] This example illustrates the preparation of Compound II(f)
in FIG. 5.
[0095] 3.15 g 1,3,5-tribromobenzene, 4.5 g 4-formylboronic acid,
0.6 g tetrakistriphenylphosphine palladium, 4.8 g potassium
carbonate, 60 mL water and 60 mL dimethoxyethane was combined under
nitrogen and refluxed for 20 hrs. After cooling to room temperature
the organic layer was collected and the aqueous layer was extracted
3.times. with 25 mL portions of methylene chloride. All extracts
and organic layer were combined and dried over magnesium sulfate
before filtering and evaporating to dryness. The resultant product
trialdehyde was isolated and characterized by nmr in yield of 3.8 g
.about.95%.
[0096] The trialdehyde material 3.8 g was combined with 9.8 g
m-diethylamino-toluene and mixed in 9 mL ethanol and 3 mL
concentrated HCl. The mixture was then gently refluxed under
nitrogen for 48 hrs. The resulting material was poured into 25 mL
water and the pH was adjusted to 8 with sodium hydroxide solution
(1N). The ethanol solvent was rotovaporated and the aqueous
supernatant was decanted from the olive green organic layer. The
organic layer was washed with 100 mL distilled water and then
triturated with dry ethanol until it became a tan colored solid.
After recrystallization from boiling ethanol, the material was
rapidly chromatographed on neutral alumina using methylene chloride
eluent to remove colored impurities and aldehyde contaminants. The
resulting white solid was collected and dried in vacuum. Yield 1.3
g .about.10%.
Example 11
[0097] This example illustrates the preparation of Compound I(t) in
FIG. 3, using the reaction scheme shown below.
##STR00001##
Precursor Compound A:
[0098] Under an atmosphere of nitrogen, a 40 mL vial was charged
with 4-bromobenzaldehyde (3.478 g, 0.0188 mol), carbazole (3.013 g,
0.0179 mol), Pd(OAc).sub.2 (0.0402 g, 1.79.times.10.sup.-4 mol),
P(t-Bu).sub.3 (0.1086 g, 5.37.times.10.sup.-4 mol), K.sub.2CO.sub.3
(7.422 g, 0.0537 mol) and 20 mL o-xylene. The reaction mixture was
heated (100 C) for two days. The resulting mixture was filtered
through a plug of silica using hexane, followed by 25% EtOAc/hexane
and finally hexane. Volatiles were evaporated to give a pale-yellow
solid, which was washed with hot MeOH (20 mL) and hexane (20 mL).
The desired product was isolated as a white powder in 29% yield
(1.406 g).
Compound I(t):
[0099] Under an atmosphere of nitrogen, a 50 mL three-neck flask
was charged with precursor compound A (1.000 g, 5.98 mmol),
N,N-diethyl-m-toluidine (2.12 mL, 11.9 mmol), conc. HCl (1 mL) and
EtOH (2 mL). The resulting mixture was refluxed for three days.
After cooling to room temperature, the solution was diluted with 25
mL H.sub.2O and adjusted the pH to 9 using 50% NaOH solution. The
volatiles were removed by rotary evaporation and the product was
purified by chromatography (7% EtOAc/hexane) to give 0.91 g (26%
yield).
Example 12
[0100] This example illustrates the preparation of Compound II(g)
in FIG. 5, using the reaction scheme shown below.
##STR00002##
[0101] Under an atmosphere of nitrogen, a round bottom flask was
charged with a THF (48 mL) solution of tris(4-bromophenyl)amine
(4.82 g, 10 mmol) and cooled to -70 C, to which nBuLi (1.6 M in
hexane, 20 mL, 32 mmol) was slowly added. After 45 minutes,
N,N-dimethylformamide (5.0 mL) was added and the reaction solution
was allowed to slowly warm up to 5 C. After quenching with HCl
(12.5 mL conc. HCl in 50 mL H.sub.2O), the resulting mixture was
allowed to stir at room temperature overnight. The aldehyde
precursor A was isolated by extraction with CH.sub.2Cl.sub.2 as a
yellow solid, which can be purified by washing with hexane to give
the pure product in 90% yield (2.97 g). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 125.33, 131.83, 133.45, 152.0,
191.17
[0102] A mixture of 3.43 g (21 mmol) of N,N-diethyl-m-toluidine,
0.988 g (3 mmol) above aldehyde precursor A in 5 mL n-propanol and
0.25 mL methane sulfonic acid were added to round-bottom flask
equipped with a Dean-Stark trap. This mixture was gently refluxed
under nitrogen for 72 h. The product, compound II(g), was isolated
as described in Example 1 to give a 1.80 g (48%) of a off-white
powder. .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 6.85 (m); 6.55 (d),
6.45 (m), 6.30 (m), 5.30 (s), 3.70 (s), 3.20 (q), 2.00 (s), 1.0
(t).
Example 13
[0103] This example illustrates the preparation of Compound II(h)
in FIG. 5, using the reaction scheme shown below.
##STR00003##
[0104] Under an atmosphere of nitrogen, a round bottom flask
equipped with a condenser was charged with Pd.sub.2(dba).sub.3
(0.88 g, 0.96 mmol), BINAP (0.62 g, 0.99 mmol), Cs.sub.2CO.sub.3
(9.38 g, 0.029 mol), 4-bromobenzaldehyde (8.17 g, 0.04 mol),
N,N'-Diphenyl-1,4-phenylenediamine (5.02 g, 0.019 mol) and toluene
(100 mL). The mixture was heated to 100 C for four days. The
reaction was cooled to room temperature, diluted with EtOAc (200
mL) and filtered through a pad of silica. Upon evaporation of
volatiles the crude material was obtained as a dark brown oil,
which was purified by silica gel chromatography (1/3 EtOAc/hexane)
to give aldeyhyde precursor C as a yellow powder in 51% yield (4.64
g). Anal. Calcd. for C.sub.32H.sub.24N.sub.2O.sub.2: C, 82.03; H,
5.16; N, 5.98. Found: C, 79.7; H, 5.40; N, 5.55.
[0105] A mixture of 1.63 g (0.01 mol) of N,N-diethyl-m-toluidine,
1.052 g (0.0022 mol) above aldehyde precursor C in 12 mL n-propanol
and 0.05 g methane sulfonic acid were added to round-bottom flask
equipped with a Dean-Stark trap. This mixture was gently refluxed
under nitrogen for 48 h. The product, compound II(h), was isolated
as described in Example 1 and was purified by extraction from hot
hexane to give a 1.03 g (42%) of a yellow powder. .sup.1H NMR
(CD.sub.2Cl.sub.2): .delta. 7.230 (t), 7.074-6.925 (m), 6.609
(broad d), 6.502 (s), 6.413 (broad d), 5.428 (s), 3.306 (d), 2.140
(s), 1.126 (t). Anal. Calcd. for C.sub.76H.sub.88N.sub.6: C, 84.09;
H, 8.17; N, 7.74. Found: C, 84.19, H, 8.37; N, 7.69.
* * * * *