DONOR-ACCEPTOR POLYMERS
20170174826 ยท 2017-06-22
Assignee
Inventors
- Qun YE (Singapore, SG)
- Ching Mui CHO (Singapore, SG)
- Wei Teng NEO (Singapore, SG)
- Jianwei XU (Singapore, SG)
Cpc classification
C08G61/126
CHEMISTRY; METALLURGY
C08G2261/3243
CHEMISTRY; METALLURGY
C08G2261/1424
CHEMISTRY; METALLURGY
C08G2261/3222
CHEMISTRY; METALLURGY
H10K85/113
ELECTRICITY
C08G61/125
CHEMISTRY; METALLURGY
C08G61/122
CHEMISTRY; METALLURGY
C08G2261/3142
CHEMISTRY; METALLURGY
H10K30/30
ELECTRICITY
H10K10/46
ELECTRICITY
H10K30/00
ELECTRICITY
C08G2261/3241
CHEMISTRY; METALLURGY
C08G2261/3223
CHEMISTRY; METALLURGY
C07D519/00
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to compounds that are electron-deficient acceptors, donor-acceptor polymers that are synthesized from such electron-deficient acceptors, semiconductor devices synthesized from such donor-acceptor polymers and methods of synthesis of such electron-deficient acceptors, donor-acceptor polymers and semiconductor devices.
Claims
1. A compound having the following Formula (I); ##STR00105## wherein P.sup.1 has the following Formula (IIa) or (IIb); ##STR00106## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X, X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N A.sup.2, A.sup.3, A.sup.4 A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and wherein P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00107## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (I).
2. A compound having repeating units of the following Formula (IV); ##STR00108## wherein P.sup.1 has the following Formula (IIA) or (IIb); ##STR00109## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00110## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH, CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (IV); P.sup.3 has the following Formula (Va), (Vb) or (Vc); ##STR00111## wherein q is 0 or 1; t is an integer selected from 1 to 4; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and P.sup.4 is absent, or is an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl. a is any value from 0 to 1; and b is an integer selected from 1 to 10,000; and y is an integer selected from 0 to 5.
3. A compound having the following Formula (VI); ##STR00112## wherein P.sup.1 has the following Formula (IIa) or (IIb); ##STR00113## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X, X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 and SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl; A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N; A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
4. A compound having the following formula (VIIa) or (VIIb); ##STR00114## wherein is a single or double bond, as valency allows; R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; and A.sup.7 is CH, CH.sub.2 or N.
5. The compound according to claim 1, wherein halogen is selected from the group consisting of F, Cl, Br and I, the optionally substituted alkyl is an optionally substituted C.sub.1-C.sub.25 alkyl, the optionally substituted alkenyl is an optionally substituted C.sub.2-C.sub.25 alkenyl, the optionally substituted alkynyl is an optionally substituted C.sub.2-C.sub.25 alkynyl, the optionally substituted cycloalkyl is an optionally substituted C.sub.3-C.sub.12 cycloalkyl, the optionally substituted heterocycloalkyl is an optionally substituted C.sub.3-C.sub.12 heterocycloalkyl, the optionally substituted cycloalkenyl is an optionally substituted C.sub.3-C.sub.12 cycloalkenyl, the optionally substituted heterocycloalkenyl is an optionally substituted C.sub.3-C.sub.12 heterocycloalkenyl, the optionally substituted aryl is an optionally substituted C.sub.3-C.sub.18 aryl and the optionally substituted heteroaryl is an optionally substituted C.sub.3-C.sub.18 heteroaryl, wherein the optionally substituted heterocycloalkyl and optionally substituted heteroaryl are independently a 3-to 18-membered monocyclic, bicyclic, or polycyclic ring, X is selected from the group consisting of halogen, CN, R.sup.1 and OR.sup.1, wherein R.sup.1 is optionally substituted alkyl, or X.sup.7 is O.
6-9. (canceled)
10. The compound according to claim 1, wherein P.sup.1 is selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodiole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothiadiazole and any combination thereof or P.sup.1 has the following Formula (IIa); ##STR00115##
11. (canceled)
12. The compound according to claim 1, wherein m is 0, wherein A.sup.1 is N, X.sup.1 is H, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are C, or X.sup.4 and X.sup.5 are independently selected from the group consisting of H, R.sup.1 and OR.sup.1, wherein R.sup.1 is optionally substituted alkyl, or wherein A.sup.1 is S; X.sup.1 is absent; A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are C, X.sup.4 and X.sup.5 are H and X is Br, or A.sup.1 is O; X.sup.1 is absent; A.sup.3, A.sup.4, A.sup.5and A.sup.6 are C, X.sup.4 and X.sup.5 are H and X is Br.
13-19. (canceled)
20. The compound according to claim 1, wherein m is 1, wherein A.sup.3 and A.sup.4 are C, X.sup.1, X.sup.2, X.sup.4 and X.sup.6 are independently absent or selected form the group consisting of H, halogen, R.sup.1 or OR.sup.1, wherein R.sup.1 is optionally substituted alkyl, A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are C or X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.6 are independently H or halogen.
21-25. (canceled)
26. The compound according to claim 1, wherein P.sup.2 is selected from the group consisting of optionally substituted imide and optionally substituted phthalamide or R.sup.2 is an optionally substituted alkyl, an optionally substituted linear alkyl or an optionally substituted branched alkyl, an optionally substituted C.sub.1 to C.sub.25 linear alkyl, or an optionally substituted C.sub.1 to C.sub.25 branched alkyl or wherein the optionally substituted branched alkyl has the following formula (XII) ##STR00116## wherein h is 0 or 1; and i and j are independently integers selected from 1 to 13, or wherein h is 1, or i is 7; and j is 9 or the optionally substituted alkyl is 2-octyldodecyl.
27-35. (canceled)
38. The compound according to claim 2, wherein P.sup.2has the following formula (IIIa): ##STR00117## or P.sup.2 has the following formula (IIIb): ##STR00118## wherein A.sup.7 is CH.sub.2 and P.sup.2 has the following formula (IIIc): ##STR00119## or A.sup.7 is CH and P.sup.2 has the following Formula (IIId): ##STR00120##
37-41. (canceled)
42. The compound according to claim 2, wherein P.sup.3 is selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted pyrrole, optionally substituted phenyl, optionally substituted fluorenes, optionally substituted carbazoles, optionally substituted fused furans and optionally substituted fused thiophenes, or P.sup.3 has the following formula (Va); ##STR00121##
43. (canceled)
44. The compound according to claim 42, wherein q is 0, or A.sup.8 is N or X.sup.8 is H, A.sup.8 is S; X.sup.8 is absent; and A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are C, X.sup.11 and X.sup.12 are taken together to form an optionally substituted 7-membered heterocycloalkyl or P.sup.3 has the following Formula (XVI); ##STR00122##
45-48. (canceled)
49. The compound according to claim 42, wherein q is 1, A.sup.10 and A.sup.13 are C, X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently selected from the group consisting of H, halogen, R.sup.3, OR.sup.3, OR.sup.10 and SR.sup.10, R.sup.3 is optionally substituted alkyl, A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are C, or R.sup.10 is an optionally substituted alkyl or has the following formula (Vb); ##STR00123## wherein A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are C, X.sup.8, X.sup.11 and X.sup.12 are H, X.sup.9 and X.sup.10 are taken together to form an optionally substituted 5-membered heterocycloalkyl, wherein the optionally substituted 5-membered heterocycloalkyl is further fused with an optionally substituted 6membered aryl, or P.sup.3 has the following formula (XVII); ##STR00124## wherein A.sup.17 is selected from the group consisting of NH, CHR.sup.11, C(R.sup.11).sub.2, SiHR.sup.11 and Si(R.sup.11).sub.2; wherein R.sup.11 is optionally substituted alkyl; wherein R.sup.11 is C.sub.8H.sub.17or C.sub.12H.sub.25.
50-62. (canceled)
63. The compound according to claim 2, wherein P.sup.3 has the following Formula (Vc); ##STR00125## wherein A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are C, X.sup.8 and X.sup.12 are H, or X.sup.10 and X.sup.11 are taken together to form an optionally substituted 5-membered heteroaryl or an optionally substituted 6-membered aryl, or P.sup.3 has the following Formula (XVIIIa) or (XVIIIb); ##STR00126## wherein A.sup.8 and A.sup.18 are independently selected from the group consisting of O, S and Se, or wherein the optionally substituted 6-membered aryl is further fused with an optionally substituted 5-membered heteroaryl, or P.sup.3 has the following Formula (XIX); ##STR00127## wherein A.sup.8 and A.sup.19 are independently selected from the group consisting of O, Se and Se; and R.sup.12 and R.sup.13 are independently selected from R.sup.14, OR.sup.14, Sr.sup.14, wherein R.sup.14 is optionally substituted alkyl, optionally substituted aryl, C.sub.8H.sub.17 or 2-ethylheptyl.
64-73. (canceled)
74. The compound according to claim 2, wherein a is 0.5, 0.3 or 0.1 or b is an integer selected from 1 to 50, or P.sup.4 is selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted pyrrole, optionally substituted phenyl, optionally substituted fluorenes, optionally substituted carbazoles, optionally substituted fused furans and optionally substituted fused thiophenes, an optionally substituted thiophene or an optionally substituted fused thiophene.
75-74. (canceled)
78. The compound according to claim 2, wherein y is 1, having the following formula (XX), (XXI), (XXII): ##STR00128## or wherein y is 2, having the following formula (XXIII), ##STR00129##
79-81. (canceled)
82. The compound according to claim 4, having the following Formula (XXIVa) or (XXIVb), ##STR00130##
83. A method for synthesizing a compound having the following Formula (VI); ##STR00131## wherein P.sup.1 has the following Formula (IIa) or (IIB); ##STR00132## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X, X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl; A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N; A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl, comprising providing a hydrazine and contacting the hydrazine with a functionalized cyclic group, wherein the cyclic group of the functionalized cyclic group is selected from the group comprising of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodiole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothidiazole and any combination thereof.
84. The method according to claim 83, wherein the functionalized cyclic group is functionalized with at least one nitrite group.
85. A method for synthesizing a compound having the following Formula (I); ##STR00133## comprising: providing a compound having the following Formula (VI); ##STR00134## and contacting a compound having the following Formula (VI); ##STR00135## with a compound having the following formula (VIIa) or (VIIb); ##STR00136## under reaction conditions to form a compound having the following Formula (I); ##STR00137## wherein P.sup.3 has the following Formula (IIa) or (IIb); ##STR00138## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X, X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N; A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and wherein P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00139## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH, CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (I); wherein
is a single or double bond, as valency allows; R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; and A.sup.7 is CH, CH.sub.2 or N.
86. The method according to claim 85, further comprising reacting a compound having repeating units of the following Formula (IV); ##STR00140## wherein P.sup.1 has the following Formula (IIa) or (IIb); ##STR00141## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N; A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00142## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH, CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (IV); P.sup.3 has the following Formula (Va), (Vb) or (Vc); ##STR00143## wherein q is 0 or 1; t is an integer selected from 1 to 4; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and P.sup.4 is absent, or is an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl, a is any value from 0 to 1; and b is an integer selected from 1 to 10,000; and y is an integer selected from 0 to 5, with N-bromosuccinimide and hydrogen peroxide, followed by a base.
87. A method for synthesizing a compound having repeating units of the following Formula (IV); ##STR00144## comprising: providing a compound having the following Formula (I); ##STR00145## and contacting a compound having the following Formula (I); ##STR00146## with; (i) a compound having the following Formula (XXVa), (XXVb) or (XXVc); ##STR00147## wherein is a single or double bond, as valency allows; q is 0 or 1; t is an integer selected from 1 to 4; X, X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and (ii) a cross-coupling reagent comprising a cyclic group; and an element selected from the group consisting of zinc, tin and boron; wherein the cyclic group is selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; in the presence of a metal-containing catalyst; wherein P.sup.1 has the following Formula (IIa) or (IIb); ##STR00148## wherein
is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00149## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH, CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (IV); P.sup.3 has the following Formula (Va), (Vb) or (Vc); ##STR00150## wherein q is 0 or 1; t is an integer selected from 1 to 4; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and P.sup.4 is absent, or is an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl, a is any value from 0 to 1; and b is an integer selected from 1 to 10,000; and y is an integer selected from 0 to 5.
88. A method for synthesizing a compound having repeating units of the following Formula (IV); ##STR00151## comprising: 1) providing a compound having the following Formula (I); ##STR00152## and 2) contacting a compound having the following Formula (I); ##STR00153## with a compound having the following Formula (XXVI); ##STR00154## wherein is a single or double bond, as valency allows; q is 0 or 1; t is an integer selected from 1 to 4; Z is a functional group containing zinc, tin or born; X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; in the presence of a metal-containing catalyst to form a monomer precursor; 3) reacting the monomer precursor of operation (2) with N-bromosuccinimide to form a reactive monomer; and 4) reacting the reactive monomer of operation (2) with a cross-coupling reagent comprising a cyclic group; and an element selected from the group consisting of zinc, tin and boron; wherein the cyclic group is selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; in the presence of a metal-containing catalyst; wherein P.sup.1 has the following Formula (IIa) or (IIb); ##STR00155## wherein
is a single or, double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00156## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH, CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (IV); P.sup.3 has the following Formula (Va), (Vb) or (Vc); ##STR00157## wherein q is 0 or 1; t is an integer selected from 1 to 4; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and P.sup.4 is absent, or is an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl, a is any value from 0 to 1; and b is an integer selected from 1 to 10,000; and y is an integer selected from 0 to 5.
89. The method of claim 88, wherein the metal in the metal-containing catalyst is selected from the group consisting of palladium, nickel and copper.
90. (canceled)
91. A semiconductor device comprising a compound having repeating units of the following Formula (IV); ##STR00158## wherein P.sup.1 has the following Formula (IIa) or (IIb); ##STR00159## wherein is a single or double bond, as valency allows; m is 0 or 1; n is an integer selected from 1 to 4; X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1; wherein R.sup.1 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkenyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted, aryl, optionally substituted heteroaryl, A.sup.1 is selected from the group consisting of O, S, Se, Te, C and N A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are independently C or N; and wherein any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; P.sup.2 has the following formula (IIIa) or (IIIb); ##STR00160## wherein R.sup.2 is an optionally substituted alkyl or optionally substituted aryl; X.sup.7 is O or S; A.sup.7 is CH, CH.sub.2 or N; and
is where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (IV); P.sup.3 has the following Formula (Va), (Vb) or (Vc); ##STR00161## wherein q is 0 or 1; t is an integer selected from 1 to 4; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 are independently absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3; wherein R.sup.3 is selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, A.sup.8 is selected from the group consisting of O, S, Se, Te, C and N A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 are independently C or N; wherein any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; and P.sup.4 is absent, or is an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl, a is any value from 0 to 1; and b is an integer selected from 1 to 10,000; and y is an integer selected from 0 to 5.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0197] The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.
[0198]
[0199]
[0200]
[0201]
[0202]
[0203]
[0204]
[0205]
[0206]
[0207]
[0208]
[0209]
[0210]
[0211]
[0212]
[0213]
[0214]
[0215]
[0216]
[0217]
[0218]
[0219]
[0220]
DETAILED DESCRIPTION OF EMBODIMENTS
[0221] A compound may have the following Formula (I);
##STR00014##
[0222] A compound may have repeating units of the following Formula (IV);
##STR00015##
[0223] A compound may have repeating units of the following formula (IVa) or (IVb):
##STR00016##
[0224] A compound may have the following Formula (VI);
##STR00017##
[0225] A compound may have the following formula (VIIa) or (VIIb);
##STR00018##
[0226] P.sup.1 may have the following Formula (IIa) or (IIb);
##STR00019##
[0227] P.sup.2 may have the following formula (IIIa) or (IIIb);
##STR00020##
[0228] P.sup.3 has the following Formula (Va), (Vb) or (Vc);
##STR00021##
[0229] P.sup.4 may be absent, or an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
[0230] may be a single or double bond, as valency allows.
[0231] m may be 0 or 1.
[0232] n may be an integer selected from 1 to 4.
[0233] X, X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may independently be absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.1, OR.sup.1 or SR.sup.1.
[0234] Halogen may be selected from the group consisting of F, Cl, Br and I.
[0235] X may be selected from the group consisting of halogen, CN, R.sup.1 and OR.sup.1.
[0236] R.sup.1 may be selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl. R.sup.1 may be an optionally substituted alkyl.
[0237] A.sup.1 may be selected from the group consisting of O, S, Se, Te, C and N.
[0238] A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may independently be C or N.
[0239] Any two substituents selected from the group consisting of X.sup.1, X.sup.2, X.sup.3, X.sup.4 and X.sup.5 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
[0240] R.sup.2 may be an optionally substituted alkyl or optionally substituted aryl.
[0241] X.sup.7 may be O or S.
[0242] A.sup.7 may be CH, CH.sub.2 or N.
[0243] may be where the compound of Formula (IIIa) or (IIIb) is fused to the compound of Formula (I) of Formula (IV).
[0244] q may be 0 or 1.
[0245] t may be an integer selected from 1 to 4.
[0246] X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be absent or selected from the group consisting of a bond, H, halogen, CN, R.sup.3, OR.sup.3 or SR.sup.3.
[0247] R.sup.3 may be selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl.
[0248] A.sup.8 may be selected from the group consisting of O, S, Se, Te, C and N.
[0249] A.sup.9, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may independently be C or N.
[0250] Any two substituents selected from the group consisting of X.sup.8, X.sup.9, X.sup.10, X.sup.11 and X.sup.12 may optionally be taken together to form an optionally substituted cyclic group selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl.
[0251] a may be any value from 0 to 1.
[0252] b may be an integer selected from 1 to 10,000.
[0253] y may be an integer selected from 0 to 5.
[0254] Optionally substituted alkyl may be an optionally substituted C.sub.1-C.sub.25 alkyl, optionally substituted alkenyl may be an optionally substituted C.sub.2-C.sub.2s alkenyl, optionally substituted alkynyl may be an optionally substituted C.sub.2-C.sub.25 alkynyl, optionally substituted cycloalkyl may be an optionally substituted C.sub.3-C.sub.12 cycloalkyl, optionally substituted heterocycloalkyl may be an optionally substituted C.sub.3-C.sub.12 heterocycloalkyl, optionally substituted cycloalkenyl may be an optionally substituted C.sub.3-C.sub.12 cycloalkenyl, optionally substituted heterocycloalkenyl may be an optionally substituted C.sub.3-C.sub.12 heterocycloalkenyl, optionally substituted aryl may be an optionally substituted C.sub.3-C.sub.18 aryl and optionally substituted heteroaryl may be an optionally substituted C.sub.3-C.sub.18 heteroaryl.
[0255] Optionally substituted heterocycloalkyl and optionally substituted heteroaryl may independently be a 3- to 18-membered monocyclic, bicyclic, or polycyclic ring.
[0256] P.sup.1
[0257] P.sup.1 may be selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodilole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothidiazole and any combination thereof.
[0258] The P.sup.1 may have the following Formula (IIa);
##STR00022## [0259] m may be 0.
[0260] A.sup.1 may be N. A.sup.1 may be S.
[0261] A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C.
[0262] X.sup.1 may be H. X.sup.1 may be absent.
[0263] X.sup.4 and X.sup.5 may independently be selected from the group consisting of H, R.sup.1 and OR.sup.1. R.sup.1 may be an optionally substituted alkyl. X.sup.4 and X.sup.5 may be H.
[0264] X may be Br.
[0265] When m is 0, A.sup.1 may be N, and X.sup.1 may be H or optionally substituted alkyl.
[0266] When m is 0, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C, and X.sup.4 and X.sup.5 are independently selected from the group consisting of H, R.sup.1 and OR.sup.1, wherein R.sup.1 is optionally substituted alkyl.
[0267] When m is 0, A.sup.1 may be S; X.sup.1 may be absent; A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C, X.sup.4 and X.sup.5 may be H and X may be Br,
[0268] When m is 0, A.sup.1 may be O; X.sup.1 may be absent; A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C, X.sup.4 and X.sup.5 may be H and X may be Br.
[0269] The compound may have the following formula (VIIIa) or (VIIIb):
##STR00023##
[0270] m may be 1.
[0271] A.sup.1, A.sup.2 A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C. A.sup.1, A.sup.2 A.sup.3 and A.sup.6 may be C. A.sup.3 and A.sup.6 may be C. A.sup.4 and A.sup.5 may be N. A.sup.4 and A.sup.5 may be C.
[0272] X.sup.1, X.sup.2, X.sup.4 and X.sup.6 may independently be absent or selected from the group consisting of H, halogen, R.sup.1 and OR.sup.1. X.sup.1, X.sup.2, X.sup.4 and X.sup.6 may independently be H or halogen. X.sup.4 and X.sup.5 may independently be H or F.
[0273] R.sup.1 may be an optionally substituted alkyl.
[0274] X.sup.1and X.sup.2 may be taken together to form an optionally substituted 5-membered heteroaryl.
[0275] When m is 1, A.sup.3 and A.sup.6 may be C and X.sup.1, X.sup.2, X.sup.4 and X.sup.6 may be independently absent or selected from the group consisting of H, halogen, R.sup.1 and OR.sup.1, wherein R.sup.1 is optionally substituted alkyl.
[0276] When m is 1, A.sup.1, A.sup.2 A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C and X.sup.1, X.sup.2, X.sup.4 and X.sup.6 may independently be H or halogen.
[0277] When m is 1, A.sup.1, A.sup.2 A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C and X.sup.1, X.sup.2, X.sup.4 and X.sup.6 may be H.
[0278] The compound may have the following Formula (VIIIc):
##STR00024##
[0279] When m is 1, A.sup.1, A.sup.2 A.sup.3 and A.sup.6 may be C and X.sup.1 and X.sup.2 may be taken together to form an optionally substituted 5-membered heteroaryl.
[0280] P.sup.1 may have the following formula (IX);
##STR00025##
[0281] A.sup.14 may be selected from the group consisting of O, S, Se, Te and N.
[0282] X.sup.14 may be absent or optionally substituted alkyl.
[0283] When P.sup.1 has the formula (IX), A.sup.4 and A.sup.5 may be N.
[0284] When P1 has the formula (IX), A.sup.4 and A.sup.5 may be C; and X.sup.4 and X.sup.5 may independently be H or F.
[0285] P.sup.1 may have the following Formula (IIb);
##STR00026##
[0286] A.sup.1, A.sup.2 A.sup.3, A.sup.4, A.sup.5 and A.sup.6 may be C.
[0287] X.sup.1, X.sup.4 and X.sup.5 may be H.
[0288] X.sup.2 and X.sup.3 may be taken together to form an optionally substituted 5-membered heterocycloalkyl. X.sup.2 and X.sup.3 may be taken together to form an optionally substituted 6-membered heterocycloalkyl. X.sup.3 and X.sup.4 may be taken together to form an optionally substituted a 6-membered aryl. X.sup.4 and X.sup.5 may be taken together to form an optionally substituted 6-membered heterocycloalkyl.
[0289] The optionally substituted 5-membered heterocycloalkyl may be further fused with an optionally substituted 6-membered aryl.
[0290] P.sup.1 may have the following formula (X);
##STR00027##
[0291] A.sup.15 may be selected from the group consisting of NH, C(R.sup.4).sub.2, and Si(R.sup.4).sub.2. R.sup.4 may be an optionally substituted alkyl.
[0292] P.sup.1 may have the following Formula (XI);
##STR00028##
[0293] X.sup.1, X.sup.15 and X.sup.16 may independently be selected from the group consisting of H, halogen and CN.
[0294] R.sup.6 and R.sup.7 may independently be selected from the group consisting of H, R.sup.8 and OR.sup.8, wherein R.sup.8 is optionally substituted alkyl.
[0295] u may be 1 or 2.
[0296] P.sup.2
[0297] P.sup.2 may be selected from the group consisting of optionally substituted imide and optionally substituted phthalamide.
[0298] R.sup.2 may be an optionally substituted alkyl. The optionally substituted alkyl may be an optionally substituted linear alkyl or an optionally substituted branched alkyl. The optionally substituted linear alkyl may be an optionally substituted C.sub.1 to C.sub.25 linear alkyl. The optionally substituted branched alkyl may be an optionally substituted C.sub.1 to C.sub.25 branched alkyl. The optionally substituted branched alkyl may have the following formula (XII).
##STR00029##
[0299] N of Formula (XII) may be where the R.sup.2 group is connected to the rest of the compound in Formulae (IVa), (IVb), (IVc), (IVd), (VIIa) or (VIIb).
[0300] h may be 0 or 1. i and j may independently be integers selected from 1 to 13. h may be 1. i may be 7. j may be 9.
[0301] The optionally substituted alkyl may be 2-ethylheptyl, 2-heptylhexadecyl, 2-heptylpentadecyl, 2-heptyltetradecyl, 2-heptyltridecyl, 2-heptyldodeclyl, 2-heptylundecyl, 2-heptyldecyl, 2-heptylnonyl, 2-heptyloctyl, 2-heptylheptyl, 2-octylhexadecyl, 2-octylpentadecyl, 2-octyltetradecyl, 2-octyltridecyl, 2-octyldodecyl, 2-octylundecyl, 2-octyldecyl, 2-octylnonyl, 2-octyloctyl, 2-nonyltetradecyl, 2-nonyltridecyl, 2-nonyldodecyl, 2-nonylundecyl, 2-nonyldecyl or 2-nonylnonyl.
[0302] The optionally substituted may be any linear or branched alkyl chain that may confer improved solubility and processability of the final product.
[0303] X7 may be O.
[0304] R2 may be an optionally substituted aryl having the following Formula (XIII);
##STR00030##
[0305] A.sup.16a, A.sup.16b, A.sup.16c, A.sup.16d and A.sup.16e may independently be selected from the group consisting of N, CH and CR.sup.9, wherein R.sup.9 is an optionally substituted alkyl. A.sup.16a may be N and A.sup.16b, A.sup.16c, A.sup.16d and A.sup.16e may be CH. A.sup.16b may be N and A.sup.16a, A.sup.16c, A.sup.16d, A.sup.16e may be CH. A.sup.16c may be N and A.sup.16a, A.sup.16b, A.sup.16d and A.sup.16e may be CH. A.sup.16b and A.sup.16d may be N and A.sup.16a, A.sup.16c, A.sup.16d and A.sup.16e may be CH. A.sup.16a, A.sup.16c, A.sup.16e may be N and A.sup.16b and A.sup.16d may be CH.
[0306] A.sup.7 may be CH. A.sup.7 may be CH.sub.2.
[0307] P.sup.2 may have the following formula (IIIa), (IIIb), (IIIc), or (IIId):
##STR00031##
[0308] The compound may have the following formula (XIV), (XVa) or (XVb):
##STR00032##
[0309] The compound of Formula (I) may be 6-alkyl-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (PPD). PPD may lower the frontier orbitals of the polymers to make the polymer more stable under ambient conditions.
[0310] P.sup.3
[0311] P.sup.3 may be a moiety that performs as a good electron donor in electrochromic materials. The chemical and physical nature of the P.sup.3 group may enhance the solubility and processability of the final polymer materials as well as the performance of the polymer films under voltage bias.
[0312] P.sup.3 may be selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted pyrrole, optionally substituted phenyl, optionally substituted fluorenes, optionally substituted carbazoles, optionally substituted fused furans and optionally substituted fused thiophenes.
[0313] P.sup.3 may have the following formula (Va);
##STR00033##
[0314] q may be 0.
[0315] A.sup.8 may be N. A.sup.8 may be S. A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C.
[0316] X.sup.8 may be H or an optionally substituted alkyl. X.sup.8 may be absent. X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, R.sup.3 and OR.sup.3. R.sup.3 may be optionally substituted alkyl.
[0317] X.sup.11 and X.sup.12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl.
[0318] When q is 0, A.sup.8 may be N, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C, Xs may be H and X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, R.sup.3 and OR3, wherein R.sup.3 is optionally substituted alkyl.
[0319] When q is 0, A.sup.8 may be S; X.sup.8may be absent; A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C and X may be Br.
[0320] When q is 0, A.sup.8 may be S; X.sup.8 may be absent; A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C, and X.sup.11 and X.sup.12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl. The optionally substituted 7-membered heterocycloalkyl may be substituted with two alkoxy groups. The alkoxy group may be OC.sub.12H.sub.25.
[0321] q may be 1.
[0322] A.sup.8, A.sup.9 A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C. A.sup.10 and A.sup.13 may be C.
[0323] X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, halogen, R.sup.3 and OR.sup.3. R.sup.3 may be an optionally substituted alkyl. X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may be independently selected from the group consisting of H, halogen, OR.sup.10 and SR.sup.10. R.sup.10 may be an optionally substituted alkyl.
[0324] When q is 1, A.sup.10 and A.sup.13 may be C; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, halogen, R.sup.3 and OR.sup.3, wherein R.sup.3 may be optionally substituted alkyl.
[0325] When q is 1, A.sup.8, A.sup.9 A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C and X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, halogen, OR.sup.10 and SR.sup.10, wherein R.sup.10 may be an optionally substituted alkyl.
[0326] P.sup.3 may be a 3,4-dialkoxythiophene.
[0327] P.sup.3 may have the following Formula (XVI);
##STR00034##
[0328] P.sup.3 may have the following formula (Vb);
##STR00035##
[0329] A.sup.8, A.sup.9 A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C.
[0330] X.sup.8, X.sup.11 and X.sup.12 may be H.
[0331] X.sup.9 and X.sup.10 may be taken together to form an optionally substituted 5-membered heterocycloalkyl.
[0332] The optionally substituted 5-membered heterocycloalkyl may be further fused with an optionally substituted 6-membered aryl.
[0333] P.sup.3 may have the following formula (XVII);
##STR00036##
[0334] A.sup.17 may be selected from the group consisting of NH, C(R.sup.11).sub.2, and Si(R.sup.11).sub.2. R.sup.11 may be optionally substituted alkyl. R.sup.11 may be C.sub.8H.sub.17.
[0335] P.sup.3 may have the following Formula (Vc);
##STR00037##
[0336] A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C. X.sup.8 and X.sup.12 may be H.
[0337] X.sup.10 and X.sup.11 may be taken together to form an optionally substituted 5-membered heteroaryl. X.sup.10 and X.sup.11 may be taken together to form an optionally substituted 6-membered aryl. The optionally substituted 6-membered aryl may be further fused with an optionally substituted 5-membered heteroaryl.
[0338] P.sup.3 may have the following Formula (XVIIIa) or (XVIIIb);
##STR00038##
[0339] A.sup.8 and A.sup.18 may be independently selected from the group consisting of O, S and Se.
[0340] P.sup.3 may have the following Formula (XIX);
##STR00039##
[0341] A.sup.8 and A.sup.19 may independently be selected from the group consisting of O, Se and Se. R.sup.12 and R.sup.13 may independently be selected from the group consisting of R.sup.14, OR.sup.14 and SR.sup.14. R.sup.14 may be optionally substituted alkyl or optionally substituted aryl. R.sup.14 may be an optionally substituted alkyl. R.sup.14 may be C.sub.8H.sub.17. R.sup.14 may be a 2-ethylheptyl group.
[0342] P.sup.4
[0343] P.sup.4 may be absent, or selected from the group consisting of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted pyrrole, optionally substituted phenyl, optionally substituted fluorenes, optionally substituted carbazoles, optionally substituted fused furans and optionally substituted fused thiophenes.
[0344] P.sup.4 may have the following formula (Va);
##STR00040##
[0345] q may be 0.
[0346] A.sup.8 may be N. A.sup.8 may be S. A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C.
[0347] X.sup.8 may be H or an optionally substituted alkyl. X.sup.8 may be absent. X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, R.sup.3 and OR.sup.3. R.sup.3 may be optionally substituted alkyl.
[0348] X.sup.11 and X.sup.12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl.
[0349] When q is 0, A.sup.8 may be N, A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C, X8 may be H and X11 and X12 may independently be selected from the group consisting of H, R3 and OR3, wherein R3 is optionally substituted alkyl.
[0350] When q is 0, A.sup.8 may be S; X.sup.8 may be absent and A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C.
[0351] When q is 0, A.sup.8 may be S; X.sup.8 may be absent; A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C and X.sup.11 and X.sup.12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl. The optionally substituted 7-membered heterocycloalkyl may be substituted with two alkoxy groups. The alkoxy groups may be OC.sub.12H.sub.25.
[0352] q may be 1.
[0353] A.sup.8, A.sup.9 A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C. A.sup.10 and A.sup.13 may be C.
[0354] X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, halogen, R.sup.3 and OR.sup.3. R.sup.3 may be an optionally substituted alkyl. X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may be independently selected from the group consisting of H, halogen, OR.sup.10 and SR.sup.10. R.sup.10 may be an optionally substituted alkyl.
[0355] When q is 1, A.sup.10 and A.sup.13 may be C; X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, halogen, R.sup.3 and OR.sup.3, wherein R.sup.3 may be optionally substituted alkyl.
[0356] When q is 1, A.sup.8, A.sup.9 A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C and X.sup.8, X.sup.9, X.sup.11 and X.sup.12 may independently be selected from the group consisting of H, halogen, OR.sup.10 and SR.sup.10, wherein R.sup.10 may be an optionally substituted alkyl.
[0357] P.sup.4 may have the following formula (Vb);
##STR00041##
[0358] A.sup.8, A.sup.9 A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C.
[0359] X.sup.8, X.sup.11 and X.sup.12 may be H.
[0360] X.sup.9 and X.sup.10 may be taken together to form an optionally substituted 5-membered heterocycloalkyl.
[0361] The optionally substituted 5-membered heterocycloalkyl may be further fused with an optionally substituted 6-membered aryl.
[0362] P.sup.4 may have the following formula (XVII);
##STR00042##
[0363] A.sup.17 may be selected from the group consisting of NH, CHR.sup.11, C(R.sup.11).sub.2, SiHR.sup.11 and Si(R.sup.11).sub.2. R.sup.11 may be optionally substituted alkyl. R.sup.11 may be C.sub.8H.sub.17 or C.sub.12H.sub.25.
[0364] P.sup.4 may have the following Formula (Vc);
##STR00043##
[0365] A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C. X.sup.8 and X.sup.12 may be H.
[0366] X.sup.10 and X.sup.11 may be taken together to form an optionally substituted 5-membered heteroaryl. X.sup.10 and X.sup.11 may be taken together to form an optionally substituted 6-membered aryl. The optionally substituted 6-membered aryl may be further fused with an optionally substituted 5-membered heteroaryl.
[0367] P.sup.4 may have the following Formula (XVIIIa) or (XVIIIb);
##STR00044##
[0368] A.sup.8 and A.sup.18 may be independently selected from the group consisting of O, S and Se.
[0369] P.sup.4 may have the following Formula (XIX);
##STR00045##
[0370] A.sup.8 and A.sup.19 may independently be selected from the group consisting of O, Se and Se. R.sup.12 and R.sup.13 may independently be selected from the group consisting of R.sup.14, OR.sup.14 and SR.sup.14. R.sup.14 may be optionally substituted alkyl or optionally substituted aryl. R.sup.14 may be an optionally substituted alkyl.
[0371] P.sup.4 may be an optionally substituted thiophene or an optionally substituted fused thiophene.
[0372] P.sup.4 may have the following Formula (XXXIa) or (XXXIb):
##STR00046##
[0373] a may be 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2 or 0.1. a may be 0.5, 0.3 or 0.1.
[0374] b may be an integer selected from 1 to 50, 1 to 10, 1 to 20, 1 to 30, 1 to 40, 10 to 20, 10 to 30, 10 to 40, 10 to 50, 20 to 30, 20 to 40, 20 to 50, 30 to 40, 30 to 50 or 40 to 50.
[0375] y may be 1. y may be 2.
[0376] The compound may have the following formula (XX):
##STR00047##
[0377] The compound may have the following formula (XXa), (XXb) or (XXc):
##STR00048##
[0378] The compound may have the following formula (XXI):
##STR00049##
[0379] The compound may have the following formula (XXIa):
##STR00050##
[0380] The compound may have the following formula (XXII):
##STR00051##
[0381] The compound may have the following formula (XXIIa):
##STR00052##
[0382] The compound may have the following formula (XXIII):
##STR00053##
[0383] The compound may have the following formula (XXIIIa):
##STR00054##
[0384] The compound may have the following Formula (XXIVa) or (XXIVb):
##STR00055##
[0385] A method for synthesizing the compound of Formula (VI) as defined above may comprise the steps of providing a hydrazine and contacting the hydrazine with a functionalized cyclic group, wherein the cyclic group of the functionalized cyclic group is selected from the group comprising of optionally substituted furan, optionally substituted thiophene, optionally substituted selenophene, optionally substituted tellurophene, optionally substituted pyrrole, optionally substituted phenylene, optionally substituted aza-phenylene, optionally substituted arylene diimide, optionally substituted fluorene, optionally substituted cabazole, optionally substituted dibenzodilole, optionally substituted benzooxodiazole, optionally substituted benzotriazole, optionally substituted benzothidiazole and any combination thereof.
[0386] The functionalized cyclic group may be functionalized with at least one nitrile (CN) group.
[0387] The functionalized cyclic group may be 2-cyanothiophene.
[0388] A method for synthesizing the compound of Formula (I) as defined above may comprise the steps of: [0389] providing the compound of Formula (IV) as defined above; and
[0390] contacting the compound of Formula (IV) as defined above with the compound (VIIa) or (VIIb) as defined above under reaction conditions to form the compound of Formula (III) as defined above. The method for synthesizing the compound of Formula (I) as defined above may comprise an inverse-electron demanding Diels-Alder reaction. An inverse-electron demanding Diels-Alder reaction is an organic chemical reaction in which two new chemical bonds and a six-membered ring are formed. It is related to the Diels-Alder reaction, whereby an organic chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, forms a substituted cyclohexene system. However, unlike the Diels-Alder reaction, the inverse electron demand Diels-Alder reaction is a cycloaddition between an electron-rich dienophile and an electon-poor diene. During an inverse-electron demand Diels-Alder reaction, three pi-bonds are broken and two sigma bonds and one new pi-bond are formed. In the present disclosure, the electronic nature of the reaction partners for an inverse Diels-Alder reaction is inversed again. The tetrazine, as the diene being used herein, may have electron-donating substituents, such as thiophenes, and is therefore considered electron-rich. The dienophile may be an intrinsically electron-poor moiety, such as an imide. This may result in synthetic challenges, which are solved by an inventive choice of solvents and reaction conditions.
[0391] The compounds of the formula (XXIVa) and (XXIVb) may both comprise electron withdrawing imides. The compounds of formula (XXIVa) and (XXIVb) may be reacted independently with the compound of Formula (I) to form the compound of Formula (III).
[0392] The compound of Formula (VIIa) or (VIIb) may be contacted with the compound of Formula (VI) to form P.sup.2 in the compound of Formula (I). When the compound of Formula (VIIa) is contacted with the compound of Formula (VI), P.sup.2 of the compound of Formula (I) may have the Formula (IIIa). When the compound of Formula (VIIb) is contacted with the compound of Formula (VI), P.sup.2 of the compound of Formula (I) may have the Formula (IIIb).
[0393] The method as defined above may be performed under reaction conditions. Reaction conditions may refer to the solvent, reaction temperature and duration of reaction. The choice of solvent, temperature and duration for the reaction for forming the compound of Formula (I) may be very important.
[0394] The solvent may be selected from the group consisting of chloroform, dichloromethane, tetrachloromethane, tetrahydrofuran, dioxane, diphenyl ether, toluene, chlorobenzene, dichlorobenzene, xylene and any mixture thereof. The solvent may not contain any reactivity towards the reaction mixture.
[0395] The reaction temperature may be in the range of about 40 C. to about 200 C., about 40 C. to about 60 C., about 40 C. to about 80 C., about 40 C. to about 100 C., about 40 C. to about 120 C., about 40 C. to about 140 C., about 40 C. to about 160 C., about 40 C. to about 180 C., about 60 C. to about 80 C., about 60 C. to about 100 C., about 60 C. to about 120 C., about 60 C. to about 140 C., about 60 C. to about 160 C., about 60 C. to about 180 C., about 60 C. to about 200 C., about 80 C. to about 100 C., about 80 C. to about 120 C., about 80 C. to about 140 C., about 80 C. to about 160 C., about 80 C. to about 180 C., about 80 C. to about 200 C., about 100 C. to about 120 C., about 100 C. to about 140 C., about 100 C. to about 160 C., about 100 C. to about 180 C., about 100 C. to about 200 C., about 120 C. to about 140 C., about 120 C. to about 160 C., about 120 C. to about 180 C., about 120 C. to about 200 C., about 140 C. to about 160 C., about 140 C. to about 180 C., about 140 C. to about 200 C., about 160 C. to about 180 C., about 160 C. to about 200 C. or about 180 C. to about 200 C. The boiling point of the solvent may be sufficiently high to allow the reaction to proceed.
[0396] The duration of reaction may be in the range of about 4 hours to about 24 hours, about 4 hours to about 6 hours, about 4 hours to about 8 hours, about 4 hours to about 10 hours, about 4 hours to about 12 hours, about 4 hours to about 18 hours, about 4 hours to about 24 hours, about 6 hours to about 8hours, about 6 hours to about 10 hours, about 6 hours to about 12 hours, about 6 hours to about 18hours, about 6 hours to about 24 hours, about 8 hours to about 10 hours, about 8 hours to about 12hours, about 8 hours to about 18 hours, about 8 hours to about 24 hours, about 10 hours to about 12hours, about 10 hours to about 18 hours, about 10 hours to about 24 hours, about 12 hours to about 18hours, about 12 hours to about 24 hours or about 18 hours to about 24 hours.
[0397] The reaction may proceed efficiently when diphenyl ether is used as the solvent and the reaction temperature is about 160 C. and the reaction duration is about 12 hours. If a solvent with a lower boiling point is used, for example, such that the reaction temperature cannot reach a sufficiently high temperature, the reaction may not proceed efficiently or at all even after 12 hours.
[0398] The method may further comprise the step of reacting the compound of Formula (III) as defined above with N-bromosuccinimide. The method may further comprise the step of reacting the compound of Formula (I) as defined above with N-bromosuccinimide and a peroxide, followed by a base when P.sup.2 of Formula (I) has the Formula (IIIc). When the P.sup.2 of the compound of Formula (I) has the Formula (IIIc), and this is reacted with N-bromosuccinimide and a peroxide, followed by a base, the resulting compound is the compound of Formula (I) where P.sup.2 has the Formula (IIId). The method may further comprise the step of reacting the compound of Formula (XVa) as defined above with N-bromosuccinimide and a peroxide, followed by a base, resulting in the formation of the compound of Formula (XVb).
[0399] The step of reacting the compound of Formula (I) as defined above with N-bromosuccinimide may be performed in a solvent selected from the group consisting of chloroform, trichloromethane, benzene and any mixture thereof.
[0400] The peroxide may be hydrogen peroxide or benzoyl peroxide. The peroxide may be benzoyl peroxide. The base may be triethylamine.
[0401] A method for synthesizing the compound of Formula (IV) as defined above may comprise the steps of: [0402] providing the compound of Formula (I) as defined above; and [0403] contacting the compound of Formula (I) as defined above with a compound having the following Formula (XVIIa), (XVIIb) or (XVIIc):
##STR00056## [0404] and a cross-coupling reagent comprising a cyclic group; and an element selected from the group consisting of zinc, tin and boron; wherein the cyclic group may be selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; in the presence of a metal-containing catalyst.
[0405] A method for synthesizing the compound of Formula (IV) as defined above, comprising the steps of: [0406] 1) providing the compound of Formula (I) as defined above; and [0407] 2) contacting the compound of Formula (I) as defined above with a compound having the following Formula (XXVI) in the presence of a metal-containing catalyst to form a monomer precursor:
##STR00057##
where Z may be a functional group containing zinc, tin or boron. Z may be Sn(CH.sub.3).sub.3 or Sn(C.sub.4H.sub.9).sub.3; [0408] 3) reacting the monomer precursor of step (2) with N-bromosuccinimide to form a reactive monomer; and [0409] 4) reacting the reactive monomer of step (2) with a cross-coupling reagent comprising a cyclic group; and an element selected from the group consisting of zinc, tin and boron; wherein the cyclic group is selected from the group consisting of an optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkenyl, optionally substituted aryl and optionally substituted heteroaryl; in the presence of a metal-containing catalyst.
[0410] When q is 0, A.sup.8 may be S; X.sup.8 may be absent; A.sup.10, A.sup.11, A.sup.12 and A.sup.13 may be C, Z may be Sn(CH.sub.3).sub.3 X.sup.10 may be H and X.sup.11 and X.sup.12 may be taken together to form an optionally substituted 7-membered heterocycloalkyl. The optionally substituted 7-membered heterocycloalkyl may be substituted with two alkoxy groups. The alkoxy groups may be OC.sub.12H.sub.25.
[0411] The compound of Formula (XXVI) may have the following formula (XXVIa):
##STR00058##
[0412] The metal in the metal-containing catalyst may be selected from the group consisting of palladium, nickel and copper. The metal-containing catalyst may be Pd(PPh.sub.3).sub.4.
[0413] The cross-coupling reagent may comprise tin. The cross-coupling reagent may comprise boron.
[0414] The cross-coupling reagent comprising tin may have the following formula (XXVII):
##STR00059##
wherein R.sup.15 may be an optionally substituted alkyl.
[0415] The cross-coupling reagent comprising boron may have the following formula (XXVIIIa);
##STR00060##
wherein R.sup.16 may be H or optionally substituted alkyl.
[0416] The cross-coupling reagent comprising boron may have the following formula (XXVIb) or (XXVIc):
##STR00061##
[0417] P.sup.3/4 may refer to P.sup.3 or P.sup.4.
[0418] The cross-coupling reagent may have the following Formula (XXIXa), (XXIXb) or (XXIXc):
##STR00062##
[0419] The cross-coupling reagent may have the following Formula (XXX):
##STR00063##
[0420] Use of the compound as defined above may be in the manufacture of semiconductor devices. A semiconductor device may comprise the compound of Formula (IV) as defined above.
EXAMPLES
[0421] Non-limiting examples of the disclosure and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.
[0422] The synthetic steps are disclosed in a general manner in the following synthetic methods. Variations of these general methods in order to produce the polymers according to the present disclosure are within the ability of the person skilled in the art. Where representative procedures are given, these can be adjusted by the person skilled in the art to other derivatives, if needed.
EXAMPLE 1
Synthesized Monomers
[0423] Pyridazines
[0424] Pyridazines synthesized having the following structure are shown in Table 1:
##STR00064##
TABLE-US-00001 TABLE 1 Pyradazine monomers Monomer name P.sup.1 R.sup.2 Monomer 1
[0425] Phthalazines
[0426] Phthalazines synthesized having the following structure are shown in Table 2:
##STR00074##
TABLE-US-00002 TABLE 2 Phthalazine monomers Monomer name P.sup.1 R.sup.2 Monomer 10
EXAMPLE 2
[0427] Some polymers synthesized from selected monomers in Tables 1 and 2 are shown in Table 3.
TABLE-US-00003 TABLE 3 Synthesized Polymers Polymer 1
[0428] For all of polymers 1 to 12, b is an integer from 1 to 50.
EXAMPLE 3
Synthesis of the Tetrazine
[0429] The synthesis of a tetrazine precursor 1 is illustrated below:
[0430] 3,6-Di(thiophen-2-yl)-1,2,4,5-tetrazine:
##STR00091##
[0431] To a dried round bottom flask (1 L) was added 2-cyanothiophene (50 grams, 0.4587 mol), hydrazine (30% concentration, 50 mL), sulphur powder (1.47 grams, 0.04587 mol) and ethanol (200 mL). The mixture was stirred at 70 C. for 3 hours before cooling down to room temperature. Brown crystals were formed at the bottom of the solution. The crystals were collected by suction filtration and washed with cold ethanol (100 mL). After complete drying, the collected crystal was loaded into a dry round bottom flask (1 L). Isoamyl nitrite (107 grams, 0.9174 mol) and chloroform (200 mL) were added into the round bottom flask. The mixture was stirred at room temperature for 6 hours. The solvent was removed by rotary evaporation and the remaining solid was recrystallized in toluene to afford the target compound as a pure red crystal. Yield=47 grams, 84%.
EXAMPLE 4
Synthesis of Polymer 1, Polymer 2 and Polymer 3
[0432] General Synthesis of the Diels-Alder Product
[0433] The general synthetic scheme for the monomer synthesis is provided in
[0434] Diels-Alder ReactionGeneral Procedure for the Synthesis of the Compounds 3 and 5
[0435] To a dry round bottom flask was added the functionalized tetrazine compound (10 mmol), the dienophile moiety (10 mmol) and appropriate solvent. The solvent may be CHCl.sub.3, DCM, THF, dioxane, toluene, chlorobenzene, dichlorobenzene, xylene, etc. The mixture was heated to reflux overnight. After it was cooled down, the mixture was poured into cold methanol and the precipitate was collected via suction filtration. It was then thoroughly washed with cold methanol and used directly for the next step without further purification.
[0436] Elimination StepGeneral Procedure for the Synthesis of the Compound 6
[0437] To a dry round bottom flask was added the substrate (8 mmol), NBS (16 mmol) and appropriate solvent (chloroform, tetrachloromethane, benzene etc.), benzoyl peroxide (1 mmol). The mixture was heated to reflux overnight. After cooling down to room temperature, the mixture was poured into methanol. The precipitate was collected and used directly for the next step without further purification to yield the brominated product.
[0438] To a dry round bottom flask was added the brominated product (4 mmol), THF (10 ml) and triethylamine (10 ml). The mixture was stirred at room temperature overnight. The organic solvent was then removed and the target molecule was obtained by silica gel column chromatography.
[0439] The Stille Cross-Coupling Reaction for Polymer 1, Polymer 2 and Polymer 3
[0440] 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (24 mg, 0.032 mmol), 6,8-dibromo-3,3-bis((dodecyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (200 mg, 0.281 mmol), and 2,5-bis(trimethylstannyI)thiophene(128 mg, 0.312 mmol) were dissolved in 12 ml of toluene, The mixture was stirred and purged with Argon for about 15 min, and then Pd(PPh.sub.3).sub.4 (18.1 mg, 0.016 mmol) was added. The flask was purged with Argon for another 15 min before the mixture was heated to 110 C. for 48 hrs. Excess solvent was removed under reduced pressure and the polymer was precipitated with methanol. The suspension was filtered to give the crude product, which was then purified by Soxhlet extraction with acetone and chloroform. The chloroform fraction was evaporated to dryness to afford a purple-red solid.
[0441] The following stoichiometric ratio relative to 2,5-bis(trimethylstannyI)thiophene was used in the polymers:
TABLE-US-00004 TABLE 4 Stoichiometric ratios of starting material in Polymers 1, 2 and 3 1,4-bis(5-bromothiophen-2- 6,8-dibromo-3,3- yl)-6-(2-octyldodecyl)-5H- bis((dodecyloxy)methyl)-3,4- pyrrolo[3,4-d]pyridazine- dihydro-2H-thieno[3,4- 5,7(6H)-dione b][1,4]dioxepine Polymer 1 0.5 0.5 Polymer 2 0.7 0.3 Polymer 3 0.9 0.1
EXAMPLE 5
Characterization of Polymer 1, Polymer 2 and Polymer 3
[0442] .sup.1H NMR Characterization
[0443] Polymer 1. Yield 68%. .sup.1H NMR (main signals) (CDCl.sub.3): 7.16-7.07 (br, s), 4.22 (br, s), 3.63-3.43 (br, m), 1.25 (br, s), 0.87 (br, s).
[0444] Polymer 2. Yield 70%. .sup.1H NMR (main signals) (CDCl.sub.3); 7.06-7.00 (br, s), 4.16 (br, s), 3.62-3.42 (br, m), 1.25 (br, s), 0.88 (br, s).
[0445] Polymer 3. Yield 50%. .sup.1H NMR (main signals) (CDCl.sub.3): 7.17-7.07 (br, s), 4.22 (br, s), 3.62-3.45 (br, m), 1.25 (br, s), 0.88 (br, s).
[0446] The GPC curves of these three polymers are shown in
[0447] UV-Vis Absorbance
[0448] The UV absorptions of solutions of the polymer 1, polymer 2 and polymer 3 in chlorobenzene in the wavelength range of 300 to 900 nm were recorded and are shown in
EXAMPLE 6
Manufacture of Devices Using Polymer 1, Polymer 2 and Polymer 3
[0449] Indium tin oxide (ITO)/glass (15/sq, 35301.1mm) were used as substrates. The substrates were cleaned by successive sonication in acetone, isopropyl alcohol and DI water for 15 minutes each. They were then blown dry using nitrogen gas. Polymer solutions of polymers 1-3 were prepared at a concentration of 10 mg/ml using a mixed solvent system chloroform and chlorobenzene in a 6:4 volume ratio. The solutions were filtered through a 0.45 m PVDF syringe filter prior to use. 80 L of the polymer solution was pipetted onto the ITO/glass substrates and a polymer film was formed from spin-coating at 500 rpm for 60 seconds. The excessive polymer edges were removed by swabbing with chloroform using a cotton bud to obtain an active area of 22 cm.sup.2. On a second piece of cleaned ITO/glass substrate, an area of 22 cm.sup.2 was blocked out using parafilm. The total thickness of the parafilm spacer was kept constant at 0.01. 250 L of the gel electrolyte (0.512 g of lithium perchlorate and 2.8 g of poly(methyl methacrylate) (MW=120,000 g/mol) in 6.65 ml of propylene carbonate and 28 ml of dry acetonitrile) was pipetted within the 22 cm.sup.2 area and left to dry for 5 minutes.
[0450] The device was fabricated by assembling the two ITO/glass substrates together with the polymer film and gel electrolyte in contact. The device was secured using parafilm. A schematic depiction of the device thus produced is shown in
EXAMPLE 7
Characterization of Devices Manufactured Using Polymer 1, Polymer 2 and Polymer 3
[0451] UV-Vis Absorbance
[0452] The UV-vis-NIR absorption spectra of the polymer devices at various applied potentials (V) for the polymer 1, polymer 2 and polymer 3 are recorded and shown in
[0453] Square-wave Potential Step Absorbance
[0454] The square-wave potential step absorptiometry of the polymer devices between 1.5 V and 1.5 V with a switch time of 10 seconds were recorded for the polymer 1, polymer 2 and polymer 3 and shown in
[0455] Optical and Electrochemical Properties
[0456]
[0457] The optical and electrochemical properties of the polymers are shown in Table 5:
TABLE-US-00005 TABLE 5 Optical and Electrochemical Properties of Polymers max, onset, max, onset, Optical solution solution film film band gap HOMO LUMO (nm) (nm) (nm) (nm) (eV) (eV) (eV) Polymer 1 532 713 530 732 1.74 5.00 3.26 Polymer 2 528 690 530 724 1.80 4.95 3.15 Polymer 3 533 660 544 699 1.88 4.92 3.04
[0458] The performance of the electrochromic devices in visible light is shown in Table 6.
TABLE-US-00006 TABLE 6 Performance of Electrochromic Devices in Visible light Coloration Contrast Bleaching Coloration Efficiency (%) Time (s) Time (s) (cm.sup.2/C.) Polymer 1 10.9 0.1 8.30 0.16 0.92 0.07 331 4 Polymer 2 12.4 0.2 7.47 0.39 0.87 0.06 282 15 Polymer 3 34.1 0.51 7.62 0.26 2.38 0.24 436 12 *Average values and standard deviations are reported based on 3 trials. Coloration refers to the process in which the percent transmittance changes from a higher value to a lower value. Bleaching refers to the process in which the percent transmittance changes from a lower value to a higher value.
[0459] The performance of the electrochromic devices in Near Infra Red (NIR) is shown in Table 7.
TABLE-US-00007 TABLE 7 Performance of Electrochromic Devices in Near Infra Red (NIR) Coloration Contrast Bleaching Coloration Efficiency (%) Time (s) Time (s) (cm.sup.2/C.) Polymer 1 36.2 1.2 0.66 0.11 8.06 0.18 454 35 Polymer 2 47.2 1.5 0.85 0.06 7.35 0.14 453 5 Polymer 3 54.2 1.4 2.24 0.24 7.12 0.42 457 14 *Average values and standard deviations are reported based on 3 trials. Coloration refers to the process in which the percent transmittance changes from a higher value to a lower value.
[0460] Bleaching refers to the process in which the percent transmittance changes from a lower value to a higher value.
EXAMPLE 8
Synthesis of Polymer 4, Polymer 5 and Polymer 6
[0461] General Synthetic Scheme
[0462] The general synthetic scheme is provided in
[0463] Diels-Alder Reaction (Synthesis of Compound 9)
[0464] 1,4-Bis(5-bromothiophen-2-yl)-7-(2-octyldodecyl)-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (9).
[0465] To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (7) (3 g, 7.43 mmol), 2-(2-octyldodecyl)-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione (8) (3.19 g, 7.43 mmol) and diphenyl ether (a) (20 ml). The mixture was purged with argon for 15 min and then heated to 160 C. for 16 h. After cooling to room temperature, the mixture was directly subjected to silica gel column chromatography. Hexane was first used to flush away the diphenyl ether. The target compound was then collected as yellow oil using mixture solvent (Hex:CHCl.sub.3=1:1) then CHCl.sub.3 as eluent (5.10 g, 82%). The product was contaminated by ca. 5% of starting material. The crude product was used for the next step without further purification. HR-APCI-MS: m/z=804.1870, calculated exact mass: 804.1862, error: 0.9 ppm.
[0466] Elimination Reaction (Synthesis of Compound 10)
[0467] 1,4-Bis(5-bromothiophen-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (10).
[0468] To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-7-(2-octyldodecyl)-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (9) (1 g, 1.25 mmol), NBS (b) (2.2 equiv. 490 mg, 2.75 mmol), benzoyl peroxide (0.1 equiv, 0.125 mmol, 30 mg) and dichloroethane (c) (20 ml). The mixture was purged with argon for 15 min and then heated to 120 C. for 2 days. After cooling to room temperature, the solvent was removed by rotary evaporation. The residue was directly subjected to silica gel column chromatography to afford the target molecule as a yellow powder (720 mg, 72%). .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=8.93 (s, 2H), 7.52-7.51 (d, 2H, J=4 Hz), 7.28-7.27 (d, 2H, J=4 Hz), 3.71-3.69 (d, 2H, J=7.2 Hz), 1.94 (m, 1H), 1.29-1.23 (m, 32H), 0.88-0.84 (m, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=166.84, 152.67, 140.05, 134.21, 131.63, 131.41, 127.56, 122.31, 119.06, 43.60, 37.41, 32.28, 31.89, 30.33, 30.02, 29.69, 26.66, 23.06, 14.50. HR-EI-MS: m/z=801.1470, calculated exact mass: 801.1456, error: 1.81 ppm.
[0469] The .sup.1H NMR, .sup.13C NMR and HRMS spectra of this compound (compound 10) are provided in
[0470] Cross-Coupling Reaction (Synthesis of Compound 12)
[0471] 1,4-Bis(5-(3,3-bis((dodecyloxy)methy)-3,4-dihydro-2H-theino[3,4-b][1,4]dioxepin-6-yl)thiophene-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (12).
[0472] To a dry round bottom flask was added (3,3-bis((dodecyloxy)methyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)trimethylstannane (11) (2 g, 50% purity), 1,4-bis(5-bromothophen-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (10) (370 mg, 0.47 mmol), Pd(PPh.sub.3).sub.4 (0.1 equiv, 0.047 mmol, 54 mg) and dry toluene (15 ml). The mixture was degassed by purging with argon and then heated to 110 C. for 16 h. After cooling to room temperature, the solvent was removed by rotary evaporation. The collected residue was dissolved in minimum amount of chloroform and directly subjected to silica gel column chromatography. The target compound was then collected as red waxy solid using a solvent mixture (Hex:CHCl.sub.3=1:1) (510 mg, 62%). The target compound was found to be unstable at ambient condition. It was stored in the fridge after preparation. .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=9.00 (s, 2H), 7.68 (d, 2H, J=3.6 Hz),7.38-7.37 (d, 2H, J=4 Hz), 6.45 (s, 2H), 4.22 (s, 4H), 4.10 (s, 4H), 3.71-3.69 (d, 2H, J=7.2 Hz), 3.55 (m, 8H), 3.44-3.41 (m, 8H), 1.94 (m, 1H), 1.68 (m, 4H), 1.56-1.54 (m, 8H), 1.30-1.24 (m, 100H), 0.88-0.85 (m, 18H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=167.06, 152.76, 150.41, 147.06, 141.15, 136.18, 134.00, 131.31, 127.99, 123.98, 122.81, 116.59, 103.85, 74.41, 72.20, 70.00, 48.25, 43.53, 37.41, 32.33, 31.89, 30.36, 30.08, 29.97, 29.77, 26.58, 23.09, 14.52. HR-APCI-MS: m/z=1744.1423, calculated exact mass: 1744.1411, error: 0.67 ppm.
[0473] Bromination Reaction (Synthesis of Compound 13)
[0474] 1,4-Bis(5-(8-bromo-3,3-bis((dodecyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]-phthalazine-6,8(7H)-dione (13).
[0475] To a dry round bottom flask was added 1,4-Bis(5-(3,3-bis((dodecyloxy)methy)-3,4-dihydro-2H-theino[3,4-b][1,4]dioxepin-6-yl)thiophene-2-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (12) (1 g, 0.573 mmol), NBS (b) (2.2 equiv., 1.26 mmol, 225 mg) and chloroform (10 ml). The mixture was stirred at room temperature overnight. The solvent was removed by rotary evaporation and the residue was directly subjected to silica gel chromatography using hexane: chloroform (1:1) to afford the target product as a red waxy solid (0.92 g, 85%). NMR (400 MHz, CDCl.sub.3): ppm=8.98 (s, 2H), 7.66-7.65 (d, J=4 Hz, 2H), 7.30-7.29 (d, J=4 Hz, 2H), 4.22 (s, 4H), 4.17 (s, 4H), 3.71-3.69 (d, J=7.2 Hz, 2H), 3.55 (s, 8H), 3.44-3.41 (t, J=6.4 Hz, 8H), 1.91 (m, 1H), 1.55-1.24 (m, 112H), 0.88-0.85 (m, 18H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=167.02, 152.76, 148.45, 145.93, 139.98, 133.99, 131.14, 127.78, 124.09, 123.11, 122.72, 116.27, 92.92, 74.67, 72.19, 69.90, 48.31, 43.53, 37.43, 32.31, 31.89, 30.35, 30.09, 26.60, 23.11, 14.54. HR-APCI-MS: m/z=1901.9589, calculated exact mass: 1901.9568, error: 1.17 ppm.
[0476] Stille Cross-coupling Polymerization.
[0477] 1,4-Bis(5-(8-bromo-3,3-bis((dodecyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4] dioxepin-6-yl)-7-(2-octyldodecyl)-6H-pyrrolo[3,4-g]-phthalazine-6,8(7H)-dione (13) (300 mg, 0.158 mmol) and bis(trimethylstannyl) compounds 14 (0.158 mmol) were dissolved in 10 ml of toluene. The mixture was stirred and purged with argon for about 15 min, and then Pd(PPh.sub.3).sub.4 (6% equiv., 0.00948 mmol, 11 mg) was added. The flask was purged with argon for another 15 min before the mixture was heated to 110 C. for 2 days. Excess solvent was removed under reduced pressure and the polymer was precipitated with methanol. The suspension was filtered to give the crude product, which was then purified by Soxhlet extraction with acetone and chloroform. The chloroform fraction was evaporated to dryness to afford the target polymer materials 15.
[0478] The bis(trimethylstannyl) compounds 14 were as follows:
##STR00092##
EXAMPLE 9
Characterization of Polymer 4, Polymer 5 and Polymer 6
[0479] .sup.1H NMR Characterization
[0480] Polymer 4. Yield 74%. .sup.1H NMR (main signals) (CDCl.sub.3): 9.09 (br), 7.92 (br), 4.31 (br, m), 3.72-3.45 (br, m), 1.68-1.58 (br, m), 1.24 (m), 0.87 (m).
[0481] Polymer 5. Yield 72%. NMR (main signals) (CDCl.sub.3): 8.99 (br), 7.65 (br), 4.33 (br), 3.62-3.48 (br, m), 1.24 (br, m), 0.86 (br, m).
[0482] Polymer 6. Yield 55%. .sup.1H NMR (main signals) (CDCl.sub.3): 9.08 (br), 7.82 (br), 6.97 (br), 4.31 (br), 3.70-3.48 (br, m), 1.79-1.68 (br), 1.24 (br), 0.86 (br).
[0483] The NMR spectra of these Polymer 4, Polymer 5 and Polymer 6 are provided in
EXAMPLE 10
Manufacture of Devices Using Polymer 4, Polymer 5 and Polymer 6
[0484] Prior to use, ITO/glass substrates were cleaned by successive ultrasonication in acetone, isopropyl alcohol and distilled water, and blown dry with N.sub.2. Polymer solutions of polymer 4, polymer 5 and polymer 6 were prepared at a concentration of 15 mg/mL in 6:4 (v/v) chloroform:chlorobenzene mixed solvent. Warm polymer solution (50 C.) was filtered and spin-coated onto the heated ITO substrates (50 C.) at 1200 rpm for 60 seconds to yield film thickness of around 100 nm. For drop-cast films, the polymer solutions are dispensed, spread onto the ITO substrates and left to dry. Film thickness of approximately 150-200 nm was obtained. Excessive polymer edges were removed by swabbing with chloroform using a cotton bud to obtain an active area of 22 cm.sup.2. On a second piece of ITO substrate, an area of 22 cm.sup.2 was blocked out using parafilm. The total thickness of the parafilm spacer and barrier was kept constant at 0.01. 250 L of the gel electrolyte (0.512 g of lithium perchlorate and 2.8 g of poly(methyl methacrylate) (MW=120,000 g/mol) in 6.65 ml of propylene carbonate and 28 ml of dry acetonitrile) was pipetted within the 22 cm.sup.2 area. The device was fabricated by assembling the two ITO/glass substrates together with the polymer film and gel electrolyte in contact.
EXAMPLE 11
Characterization of Devices Manufactured Using Polymer 4, Polymer 5 and Polymer 6
[0485] Electron Capture (EC) Electrospectroscopy
[0486] The electron capture (EC) electrospectroscopy of the polymer 5 in a EC device is depicted in
[0487]
[0488] The electrochromic performance of the polymer devices of Polymer 4, Polymer 5 and Polymer 6 are summarized in the following Table 8:
TABLE-US-00008 TABLE 8 Electrochromic performance of Devices Comprising Polymers 4, 5 and 6 Optical contrast Bleaching Coloration CE (%) time (s) time (s) (cm.sup.2/C.) 1400 1400 1400 1400 max nm max nm max nm max nm Polymer 4 11 58 23.2 17.6 4.0 23.6 205 379 Polymer 5 34 71 23.0 2.59 1.8 17.7 471 651 Polymer 6 14 62 25.3 17.9 4.5 23.6 274 366
[0489] The optical contrast refers to how much the color of the film has changed upon an applied voltage. Polymers 4, 5 and 6 showed reasonably good optical contrast in the visible region and good contrast in the NIR region. The bleaching time and coloration time refer to how fast the device changes its color. Polymers 4, 5 and 6 showed good coloration time below 5 seconds. This means that upon an applied voltage, the thin film device will reach their full optical contrast in less than 5 seconds. The coloration efficiency describes how much electricity is needed to power the polymer device. The coloration efficiency for this batch of polymers is generally good with values greater than 200 cm.sup.2/C.
EXAMPLE 12
Time-Dependent Density Functional Theory Calculation
[0490] Time-dependent density-functional theory calculation is carried out to compare the magnitude of electron deficiency of the imide-fused pyridazines with current commonly used electron deficient acceptors. The results shown in
EXAMPLE 13
[0491] Monomer 1:
##STR00093##
[0492] 1,4-Bis(5-bromothiophen-2-yl)-6-hexyl-5H-pyrrolo[3,4-d]-pyridazine-5,7(6H)-dione
[0493] To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (300 mg, 0.743 mmol), 1-(2-hexyl)-1H-pyrrole-2,5-dione (135 mg, 0.743 mmol) and diphenyl ether (10 ml). The mixture was purged with argon for 15 min and then heated to 160 C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl.sub.3=1:1) then CHCl.sub.3 as eluent (230 mg, 56%). .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=8.62-8.61 (d, J=4 Hz, 2H), 7.20-7.18 (d, J=3.6 Hz, 2H), 3.79-3.76 (t, J=7.6 Hz, 2H), 1.72-1.67 (m, 2H), 1.33 (m, 6H), 0.91-0.87 (t, J=6.4 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=167.47, 148.32, 139.74, 134.33, 132.09, 122.57, 121.47, 39.64, 31.66, 28.58, 26.92, 22.87, 14.40. HR-EI-MS: m/z=552.9136, calculated exact mass: 552.9123, error: 2.28 ppm.
[0494] Monomer 3:
##STR00094##
[0495] 1,4-Bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione:
[0496] To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (3 g, 7.43 mmol), 1-(2-octyldodecyl)-1H-pyrrole-2,5-dione (2.8 g, 7.43 mmol) and diphenyl ether (20 ml). The mixture was purged with argon for 15 min and then heated to 160 C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl.sub.3=1:1) then CHCl.sub.3 as eluent (3.42 g, 62%). .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=8.63-8.62 (d, J=4 Hz, 2H), 7.19-7.18 (d, J=4 Hz, 2H), 3.67-3.65 (d, J=7.2 Hz, 2H), 1.90 (m, 1H), 1.25-1.24 (m, 32H), 0.89-0.85 (m, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=167.72, 148.30, 139.78, 134.38, 132.09, 122.47, 121.47, 43.81, 37.37, 32.31, 32.27, 31.85, 30.31, 30.02, 29.97, 29.93, 29.75, 29.68, 26.62, 23.08, 14.52. HR-EI-MS: m/z=750.1408, calculated exact mass: 750.1393, error: 2.1 ppm.
[0497] Monomer 4:
##STR00095##
[0498] 1,4-Bis(5-bromofuran-2-yl)-6-hexyl-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione:
[0499] To a dry round bottom flask was added 3,6-bis(5-bromofuran-2-yl)-1,2,4,5-tetrazine (300 mg, 0.81 mmol), 1-(2-hexyl)-1H-pyrrole-2,5-dione (146 mg, 0.81 mmol) and diphenyl ether (10 ml). The mixture was purged with argon for 15 min and then heated to 160 C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl.sub.3=1:1) then CHCl.sub.3 as eluent (310 mg, 73%). .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=8.03-8.02 (d, J=3.6 Hz, 2H), 6.62-6.61 (d, J=4 Hz, 2H), 3.77-3.73 (t, J=7.6 Hz, 2H), 1.70-1.65 (m, 2H), 1.32 (m, 6H), 0.89-0.86 (t, J=6.4 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=167.72, 148.30, 139.78, 134.38, 132.09, 122.47, 121.47, 43.81, 37.37, 32.31, 32.27, 31.85, 30.31, 30.02, 29.97, 29.93, 29.75, 29.68, 26.62, 23.08, 14.52. HR-EI-MS: m/z=520.9586, calculated exact mass: 520.9580, error: 1.04 ppm.
[0500] Monomer 6:
##STR00096##
[0501] 1,4-Bis(5-bromofuran-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione:
[0502] To a dry round bottom flask was added 3,6-bis(5-bromofuran-2-yl)-1,2,4,5-tetrazine (1.48 g, 4 mmol), 1-(2-octyldodecyl)-1H-pyrrole-2,5-dione (4 mmol, 1.51 g) and diphenyl ether (15 ml). The mixture was degassed by purging with argon and then heated to 160 C. for 16 h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl.sub.3=1:1) then CHCl.sub.3 as eluent (1.86 g, 65%). .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=8.06 (d, 2H, J=3.6 Hz), 6.64-6.63 (d, 2H, J=3.6 Hz), 3.66-3.64 (d, 2H, J=7.6 Hz), 1.57 (m, 1H), 1.24 (m, 32H), 0.89-0.85 (m, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=166.89, 149.69, 143.31, 128.45, 122.25, 121.37, 115.17, 43.77, 37.29, 32.30, 31.81, 30.30, 30.01, 29.73, 29.67, 26.59, 23.07, 14.51. HR-EI-MS: m/z=719.1476, calculated exact mass: 719.1756, error: 1.41 ppm.
[0503] Monomer 10Step 1:
##STR00097##
[0504] 1,4-Bis(5-bromothiophen-2-yl)-7butyl-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione:
[0505] To a dry round bottom flask was added 3,6-bis(5-bromothiophen-2-yl)-1,2,4,5-tetrazine (400 mg, 0.1 mmol), 2-butyl-3a,4,7,7a-tetrahydro-1H-isoindole 1,3(2H)-dione (207 mg, 0.1 mmol) and diphenyl ether (10 ml). The mixture was purged with argon for 15 min and then heated to 160 C. for 16h. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Hexane was used first to flush away the diphenyl ether. The target compound was then collected as yellow powder using mixture solvent (Hex:CHCl.sub.3=1:1) then CHCl.sub.3 as eluent (410 mg, 71%). .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=7.32-7.31 (d, J=4 Hz, 2H), 7.16-7.15 (d, J=4 Hz, 2H), 3.83-3.79 (m, 2H), 3.44-3.42 (m, 2H), 3.38-3.35 (t, J=6.8 Hz, 2H), 2.94-2.90 (m, 2H), 1.27-1.22 (m, 2H), 0.74-0.70 (t, J=6.8 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=178.33, 151.97, 140.45, 133.24, 131.26, 129.88, 117.50, 39.39, 38.88, 29.69, 25.21, 19.85, 13.80. HR-EI-MS: m/z=580.9288, calculated exact mass: 580.9265, error: 3.94 ppm.
[0506] The HR-EI MS spectrum for this intermediate is shown further below as
[0507] Monomer 10Step 2:
##STR00098##
[0508] 1,4-Bis(5-bromothiophen-2-yl)-7-butyl-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione:
[0509] To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-7-butyl-5,5a,8a,9-tetrahydro-6H-pyrrolo[3,4-g]phthalazine-6,8(7H)-dione (200 mg, 0.345 mmol), NBS (2.2 equiv., 0.76 mmol, 135 mg), BPO (0.1 equiv. 0.0345 mol, 10 mg) and dichloroethane (10ml). The mixture was purged with argon for 10 min and then heated to 120 C. for 2 days. After cooling to room temperature, the mixture was directly subject to silica gel column chromatography. Chloroform was used as the eluent and the target product was obtained as a yellow solid. (135 mg, 68%) .sup.1H NMR (400 MHz, CDCl.sub.3): ppm=.8.92 (s, 2H), 7.52-7.51 (d, J=4 Hz, 2H), 7.29-7.28 (d, J=3.6 Hz, 2H), 3.83-3.80 (t, J=7.2 Hz, 2H), 1.76-1.68 (m, 2H), 1.45-1.37 (m. 2H), 0.99-0.95 (t, J=7.6 Hz, 3H) .sup.13C NMR (100 MHz, CDCl.sub.3): ppm=166.52, 152.63, 139.69, 134.39, 131.69, 131.61, 127.66, 122.35, 119.26, 39.14, 30.82, 20.49, 14.00. HR-EI-MS: m/z=572.8961, calculated exact mass: 576.8952, error: 1.65 ppm.
EXAMPLE 14
Further Experimental Examples Relating to the Polymer Syntheses
[0510] Polymer 7:
##STR00099##
[0511] To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), 2,2-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(1,3,2-dioxaborinane) (168 mg, 0.3 mmol), Pd(PPh.sub.3).sub.4 (6 mol %, 0.018 mmol, 21 mg), K.sub.2CO.sub.3 (2 mmol, 276 mg), H.sub.2O (1 ml), toluene (10 ml) and Aliquat 336 (catalytic amount). The mixture was purged with argon for 30 min and then heated to 100 C. for 48 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The red precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (250 mg, 85%)
[0512] Polymer 8:
##STR00100##
[0513] To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), 9-(2-dodecyl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (210 mg, 0.3 mmol), Pd(PPh.sub.3).sub.4 (6 mol %, 0.018 mmol, 21 mg), K.sub.2CO.sub.3 (2 mmol, 276 mg), H.sub.2O (1 ml), toluene (10 ml) and Aliquat 336 (catalytic amount). The mixture was purged with argon for 30 min and then heated to 100 C. for 48 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The purple precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (250 mg, 85%)
[0514] Polymer 9:
##STR00101##
[0515] To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), (4,8-bis(octyloxy)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd.sub.2(dba).sub.3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol).sub.3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100 C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (230 mg, 74%)
[0516] Polymer 10:
##STR00102##
[0517] To a dry round bottom flask was added 1,4-bis(5-bromofuran-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (216 mg, 0.3 mmol), (4,8-bis(octyloxy)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd.sub.2(dba).sub.3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol).sub.3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100 C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (215 mg, 72%)
[0518] Polymer 11:
##STR00103##
[0519] To a dry round bottom flask was added 1,4-bis(5-bromothiophen-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (225 mg, 0.3 mmol), (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd.sub.2(dba).sub.3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol).sub.3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100 C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (210 mg, 68%)
[0520] Polymer 12:
##STR00104##
[0521] To a dry round bottom flask was added 1,4-bis(5-bromofuran-2-yl)-6-(2-octyldodecyl)-5H-pyrrolo[3,4-d]pyridazine-5,7(6H)-dione (216 mg, 0.3 mmol), (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (232 mg, 0.3 mmol), Pd.sub.2(dba).sub.3 (3 mol %, 0.009 mmol, 8.5 mg), P(o-tol).sub.3 (12 mol %, 0.036 mmol, 11 mg) and toluene (10 ml). The mixture was purged with argon for 30 min and then heated to 100 C. for 16 h. After cooling to room temperature, chloroform was added to dilute the solution and then extraction with water was done for three times. The organic layer was collected and dried by rotary evaporation. The residue was dissolved in minimal amount of chloroform and precipitated into methanol solution. The precipitate was collected via suction filtration. The polymer was purified by Soxhlet extraction with hexane for 20 h, followed by acetone for 20 h and finally washed down by chloroform. The chloroform part was concentrated and dropped into methanol solution with rigorous stirring. The precipitate was collected via suction filtration, thoroughly washed with methanol and dried under vacuum. (200 mg, 67%)
INDUSTRIAL APPLICABILITY
[0522] The compounds of Formula (VI), (VIIa) and (VIIb) as defined above may be useful in the manufacture of the compounds of Formula (I). The compound of Formula (I) may be useful in the manufacture of the compounds of Formula (IV). The compounds of Formula (IV) may be useful in the manufacture of semiconductor devices. The semiconductor devices manufactured using the compound of Formula (IV) as defined above may be used in a wide range of applications such as electrochromic materials, organic light-emitting diode, organic thin-film transistors and organic photovoltaic cells. As the NIR absorption properties can be reversibly switched by applying/removing a low voltage on the thin film, the materials may have applications in smart glass or smart window applications.
[0523] It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.