Luminescent compositions and their uses
View Patent ↗High quantum yield luminescent monomers, oligomers, and polymers, comprising benzotriazole repeating units and derivatives thereof have been discovered and utilized in optical devices and components therefor, including electroluminescent devices, light emitting devices, photoluminescent devices, organic light emitting diodes (OLEDs), OLED displays, sensors, and the like.
1. A polymer or oligomer comprising:
(a) at least one type of a constitutional repeating unit of the general formula selected from the group consisting of Formula I and Formula II, represented below, said constitutional repeating unit having a benzotriazole type group, either as part of the main chain or as a side chain
b) at least one type of a constitutional repeating unit of the general formula represented below by Formula III in the amount of 75 mol % or less:
wherein
R is H, D, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, 2-hydroxyphenyl, 2-alkoxyphenyl, 2-aryloxyphenyl, substituted 2-hydroxyphenyl, substituted 2-alkoxyphenyl, substituted 2-aryloxyphenyl, fluoroalkyl, or fluoroaryl;
A 1 is C, when said benzotriazole type group is linked at A 1 , or A 1 is CH, CR 1 , or N, when said benzotriazole type group is not linked at A 1 ;
A 2 is C, when said benzotriazole type group is linked at A 2 , or A 2 is CH, CR 2 , or N, when said benzotriazole type group is not linked at A 2 ;
A 3 is C, when said benzotriazole type group is linked at A 3 , or A 3 is CH, CR 3 , or N, when said benzotriazole type group is not linked at A 3 ;
A 4 is CH, CR 4 , or N, when said benzotriazole type group is not linked at A 4 , or A 4 is C, when said benzotriazole type group is linked at A 4 ;
J is a trivalent moiety selected from the group consisting of 1,2,4-phenylenetriyl and >CR 6 CR 7 R 8 —;
G is nil or is selected from the group consisting of —Ar—, —O—, —S—, —NR 1 —, CR 2 R 3 —, —CR 1 R 2 CR 3 R 4 —, N═CR 1 —, CR 1 ═CR 2 —, —N═N—, —(CO)—, C 3 to C 30 alkyldiyl, and C 3 to C 30 heteroalkyldiyl;
Q is selected from the group consisting of —Ar—, —O—, —S—, —NR 1 —, —OCR 1 R 2 —, —CR 1 R 2 —, —OCR 1 R 2 CR 3 R 4 —, —CR 1 R 2 CR 3 R 4 —, —N═CR 1 —, —CR 1 ═N—, —CR 1 ═CR 2 —, —N═N—, and —(CO)—, —BR 1 —, SiR 1 R 2 —, —(CO)—O—, —O—(CO)—, —NR 1 —(CO)—, and —(CO)—NR 1 —, C 3 to C 30 alkyldiyl, and C 3 to C 30 heteroalkyldiyl;
R 1 , R 2 , R 3 , R 4 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and any two of adjacent R 1 , R 2 , R 3 or R 4 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran;
R 6 , R 7 , and R 8 are each independently substituted or unsubstituted alkyl or aryl; and any two of adjacent R 6 , R 7 , R 8 , are optionally bridging; and
Ar is unsubstituted or substituted, single or multiple ring, fused or non-fused aromatic or heteroaromatic.
2. The polymer or oligomer of claim 1 comprising at least one type of a constitutional repeating unit of Formula IV, Formula V or Formula VI represented below:
wherein
R is H, D, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, 2-hydroxyphenyl, 2-alkoxyphenyl, 2-aryloxyphenyl, substituted 2-hydroxyphenyl, substituted 2-alkoxyphenyl, substituted 2-aryloxyphenyl, fluoroalkyl, or fluoroaryl;
A 5 is CH, CR 1 , or N;
A 6 is CH, CR 2 , or N;
A 7 is CH, CR 3 , or N;
A 8 is CH, CR 4 , or N;
R 1 , R 2 , R 3 , R 4 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and any two of adjacent R 1 , R 2 , R 3 or R 4 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl and are optionally bridging.
3. The polymer or oligomer of claim 2 comprising at least one type of a constitutional repeating unit of Formula VII represented below:
wherein
R is H, D, alkyl, aryl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, 2-hydroxyphenyl, 2-alkoxyphenyl, 2-aryloxyphenyl, substituted 2-hydroxyphenyl, substituted 2-alkoxyphenyl, substituted 2-aryloxyphenyl, fluoroalkyl, or fluoroaryl.
4. The polymer or oligomer of claim 3 , wherein
R is
s is 0-5;
R 15 is selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and when s is 2-5, any two of adjacent R 15 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl and are optionally bridging.
5. The polymer or oligomer of claim 4 , wherein
R is selected from the group consisting of:
R 50 and R 51 are each independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, fluoroalkyl, fluoroaryl, amide, and ester; and
R 52 is selected from the group consisting of alkyl, aryl, heteroaryl, fluoroalkyl, and fluoroaryl.
6. The polymer or oligomer of claim 5 , wherein
R is selected from the group consisting of:
7. The polymer or oligomer of claim 3 , wherein R is alkyl.
8. The polymer or oligomer of claim 7 , wherein R is n-hexyl.
9. The polymer or oligomer of claim 1 , containing at least one type of a constitutional repeating unit of the general formula represented below by Formula III:
wherein
Q is selected from the group consisting of:
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, aryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, and any two of adjacent R 5 groups are optionally bridging;
p is 0-2;
q is 0-3;
r is 0-4;
s is 0-5;
t is 0-6;
X and Y are each independently selected from the group consisting of —O—, —S—, —NR 6 —, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, —N═CR 6 —, —CR 6 ═CR 7 —, —N═N—, and —(CO)—;
Z is selected from the group consisting of —O—, —S—, —NR 6 —, aryl, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, oxazole, oxadiazole, thiazole, thiadiazole, substituted triazole, tetrazole, tetrazine, triazine, substituted triazine, linear, dendrimeric or hyperbranched polymeric, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, N═CR 6 —, CR 6 ═CR 7 —, —N═N—, and —(CO)—;
R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic, and any two of adjacent R 6 , R 7 , R 8 , and R 9 are optionally bridging;
E is selected from the group consisting of O, NH, and S;
A 1 is C, when group is linked at A 1 , or A 1 is CH, CR 1 , or N, when group is not linked at A 1 ;
A 2 is C, when group is linked at A 2 , or A 2 is CH, CR 2 , or N, when group is not linked at A 2 ;
A 3 is C, when group is linked at A 3 , or A 3 is CH, CR 3 , or N, when group is not linked at A 3 ; and
A 4 is C, when group is linked at A 4 , or A 4 is CH, CR 4 , or N, when group is not linked at A 4 .
10. The polymer or oligomer of claim 1 , wherein Q is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, —C(O)NH—, —CH 2 —CH 2 —, —CH 2 CH 2 O—, CH2CH 2 CH 2 CH 2 O—, CH 2 CHCONH 2 —, —CH 2 CH(CN)—, —CH 2 CH═CHCH 2 —, —CONHCO—, —CH 2 CH(OOCCH 3 )—, —CH 2 CHCl—, —CH 2 CHOH—, —CH(OCH 2 CH 3 )CH 2 —, —CH(OCH 2 CH(CH 3 ) 2 )CH 2 —, —CH 2 C(CH 3 )(C(O)OCH 3 )—, —CH2C(CH3)(C(O)OH—, —NHC(O)NH—, —OC(O)NH—, —C(S)—, —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCH 2 CH 2 —, —CH 2 OCH 2 —, —CH 2 CH 2 O—, —OCH 2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 —, —CH 2 CH 2 OCH 2 —, —CH 2 CH 2 CH 2 O—, —OCH 2 CH 2 CH 2 CH 2 —, —CH 2 OCH 2 CH 2 CH 2 —, —CH 2 CH 2 OCH 2 CH 2 —, —CH 2 CH 2 CH 2 OCH 2 —, —CH 2 CH 2 CH 2 CH 2 O—, —C(O)NHCH 2 —, —C(O)NHCH 2 CH 2 —, —CH 2 C(O)NHCH 2 —, —CH 2 CH 2 C(O)NH—, —C(O)NHCH 2 CH 2 CH 2 —, —CH 2 C(O)NHCH 2 CH 2 —, —CH 2 CH 2 C(O)NHCH 2 —, —CH 2 CH 2 CH 2 C(O)NH—, —C(O)NHCH 2 CH 2 CH 2 CH 2 —, —CH 2 C(O)NHCH 2 CH 2 CH 2 —, —CH 2 CH 2 C(O)NHCH 2 CH 2 —, —CH 2 CH 2 CH 2 C(O)NHCH 2 —, —CH 2 CH 2 CH 2 C(O)NHCH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 C(O)NH—, —C(O)OCH 2 —, —CH 2 C(O)OCH 2 —, —CH 2 CH 2 C(O)OCH 2 —, —C(O)OCH 2 CH 2 —, —NHC(O)CH 2 —, —CH 2 NHC(O)CH 2 —, —CH 2 CH 2 NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, —CH 2 NHC(O)CH 2 CH 2 —, —CH 2 CH 2 NHC(O)CH 2 CH 2 —, —C(O)NHCH 2 —, —C(O)NHCH 2 CH 2 —, —OC(O)NHCH 2 —, —OC(O)NHCH 2 CH 2 —, —OC(O)NHCH 2 CH 2 CH 2 —, —NHCH 2 —, —NHCH 2 CH 2 —, —CH 2 NHCH 2 —, —CH 2 CH 2 NHCH 2 —, —C(O)CH 2 —, —C(O)CH 2 —CH 2 —, —CH 2 C(O)CH 2 —, —CH 2 CH 2 C(O)CH 2 —, —CH 2 CH 2 C(O)CH 2 CH 2 —, —CH 2 CH 2 C(O)—, —CH 2 CH 2 CH 2 C(O)NHCH 2 CH 2 NH—, —CH 2 CH 2 CH 2 C(O)NHCH 2 CH 2 NHC(O)—, —CH 2 CH 2 CH 2 C(O)NHCH 2 CH 2 NHC(O)CH 2 —, —CH 2 CH 2 CH 2 C(O)NHCH 2 CH 2 NHC(O)CH 2 CH 2 —, —OC(O)NH(CH 2 ) 0-6 (OCH2CH2) 0-2 -, —C(O)NH(CH 2 ) 1-6 NHC(O)—, —NHC(O)NH(CH 2 ) 1-6 —NH—C(O)—, —OC(O)CH 2 —, —O—C(O)CH 2 CH 2 —, and —OC(O)CH 2 CH 2 CH 2 —.
11. The polymer or oligomer of claim 9 , wherein Q is
wherein
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging; and
r is 0-4.
12. The polymer or oligomer of claim 11 , wherein Q is
13. The polymer or oligomer of claim 6 or 8 , comprising at least one type of a constitutional repeating unit of the general formula represented below by Formula III:
wherein Q is
14. The polymer or oligomer of claim 11 , wherein Q is
15. The polymer or oligomer of claim 6 or 8 comprising at least one constitutional repeating unit of the general formula represented below Formula III:
wherein Q is
16. The polymer or oligomer of claim 6 or 8 , comprising at least two different types of constitutional repeating units of the general formula represented below by Formula III:
wherein at least one of the two different types of constitutional repeating units is selected from the group consisting of
17. The polymer or oligomer of claim 9 , wherein Q is
wherein
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging;
p is 0-2;
X is selected from the group consisting of —O—, —S—, —NR 6 —, and CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, —N═CR 6 —, —CR 6 ═CR 7 —, —N═N—, and —(CO)—; and
R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic, and any two of adjacent R 6 , R 7 , R 8 , and R 9 are optionally bridging.
18. The polymer or oligomer of claim 17 , wherein
Q is
A 6 is CH, CR 2 , or N;
A 7 is CU, CR 3 , or N;
R 2 and R 3 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and R 2 and R 3 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl and are optionally bridging.
19. The polymer or oligomer of claim 18 , wherein Q is
20. The polymer or oligomer of claim 6 or 8 , comprising at least one type of a constitutional repeating unit of the general formula represented below by Formula III:
wherein
Q is
A 6 is CH, CR 2 , or N;
A 7 is CH, CR 3 , or N;
R 2 and R 3 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and R 2 and R 3 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl and are optionally bridging.
21. The polymer or oligomer of claim 6 or 8 , comprising at least one type of a constitutional repeating unit of the general formula represented below by Formula III:
wherein Q is
22. The polymer or oligomer of claim 21 , comprising further at least three different types of constitutional repeating units of the general formula represented below Formula III:
wherein at least one of the three different types of constitutional repeating units is selected from the group consisting of
23. The polymer or oligomer of claim 9 , wherein
Q is
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, and any two of adjacent R 5 groups are optionally bridging; and
t is 0-6.
24. The polymer or oligomer of claim 23 , wherein Q is
25. The polymer or oligomer of claim 6 or 8 , comprising at least one constitutional repeating unit of the general formula represented below by Formula III:
wherein Q is
26. The polymer or oligomer of claim 9 , wherein
Q is
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, and any two of adjacent R 5 groups are optionally bridging;
R 6 is selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic; and
q is 0-3.
27. The polymer or oligomer of claim 26 , wherein Q is
28. The polymer or oligomer of claim 6 or 8 , wherein Q is
29. The polymer or oligomer of claim 6 or 8 , comprising at least two different types of constitutional repeating units of the general formula represented below by Formula III:
wherein at least one Q is selected from the group consisting of
30. The polymer or oligomer of claim 9 , wherein
Q is
R 5 is each independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, and any two of adjacent R 5 groups are optionally bridging;
q is 0-3;
X is selected from the group consisting of —O—, —S—, —NR 6 —, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, —N═CR 6 —, CR 6 ═CR 7 —, —N═N—, and —(CO)—; and
R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic, and any two of adjacent R 6 , R 7 , R 8 , and R 9 are optionally bridging.
31. The polymer or oligomer of claim 30 , wherein Q is
32. The polymer or oligomer of claim 6 or 8 , wherein Q is
33. The polymer or oligomer of claim 9 , wherein
Q is
R 5 is each independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging,
R 6 is selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic; and
r is 0-4.
34. The polymer or oligomer of claim 33 , wherein Q is
35. The polymer or oligomer of claim 6 or 8 , comprising at least two constitutional repeating units of the general formula represented below by Formula III:
wherein at least one Q is selected from the group consisting of
36. The polymer or oligomer of claim 6 or 8 , comprising at least two types of constitutional repeating units of the general formula represented below by Formula III:
wherein at least one Q is selected from the group consisting of
37. The polymer or oligomer of claim 6 or 8 , comprising at least one type of a constitutional repeating unit of the general formula represented below by Formula III:
wherein Q is
38. The polymer or oligomer of claim 6 or 8 , comprising at least two constitutional repeating units of the general formula represented below by Formula III:
wherein at least one Q is selected from the group consisting of
39. The polymer or oligomer of claim 9 , wherein
Q is
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging; and
r is 0-4;
X is selected from the group consisting of —O—, —S—, —NR 6 —, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, —N═CR 6 —, CR 6 ═CR 7 , —N═N—, and —(CO)—;
R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic, and any two adjacent R 6 , R 7 , R 8 , and R 9 are optionally bridging.
40. The polymer or oligomer of claim 6 or 8 , wherein
Q is
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging; and
r is 0-4;
X is selected from the group consisting of —O—, —S—, —NR 6 —, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, —N═CR 6 —, CR 6 ═CR 7 —, —N═N—, and —(CO)—;
R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic, and any two adjacent R 6 , R 7 , R 8 , and R 9 are optionally bridging.
41. The polymer or oligomer of claim 1 wherein said polymer or oligomer comprises a constitutional repeating unit selected from the group consisting of
wherein
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent (geminal, vicinal, or ortho) R 5 groups are optionally bridging;
J is a trivalent moiety selected from the group consisting of 1,2,4-phenylenetriyl and >CR 6 CR 7 R 8 —;
G is nil or is selected from the group consisting of —Ar—, —O—, —S—, —NR 1 —, CR 2 R 3 —, —CR 1 R 2 CR 3 R 4 —, N═CR 1 , CR 1 ═CR 2 —, —N═N—, —(CO)—, C 3 to C 30 alkyldiyl, and C 3 to C 30 heteroalkyldiyl;
R 1 , R 2 , R 3 , R 4 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and any two of adjacent (geminal, vicinal, or ortho) R 1 , R 2 , R 3 or R 4 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran;
R 6 , R 7 , and R 8 are each independently substituted or unsubstituted alkyl or aryl; and any two of adjacent R 6 , R 7 , R 8 , are optionally bridging;
Ar is unsubstituted or substituted, single or multiple ring, fused or non-fused aromatic or heteroaromatic; and
r is 0-4.
42. The polymer or oligomer of claim 41 , wherein J is >CHCH 2 —.
43. The polymer or oligomer of claim 1 wherein said polymer is comprised of a constitutional repeating unit selected from the group consisting of
wherein
R is H, D, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, 2-hydroxyphenyl, 2-alkoxyphenyl, 2-aryloxyphenyl, substituted 2-hydroxyphenyl, substituted 2-alkoxyphenyl, substituted 2-aryloxyphenyl, fluoroalkyl, or fluoroaryl;
R 1 and R 2 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic;
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging;
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl, and are optionally bridging;
Ar is unsubstituted or substituted, single or multiple ring, fused or non-fused aromatic or heteroaromatic; and
r is 0-4.
44. The polymer or oligomer of claim 1 wherein said polymer is comprised of a constitutional repeating unit represented below
45. The polymer or oligomer of claim 1 comprising:
(a) about 25 mol % of at least one constitutional repeating unit of the general formula selected from the group consisting of Formula I and Formula II; and
(b) about 75 mol % of at least one constitutional repeating unit of the general formula represented by Formula III.
46. The polymer or oligomer of claim 1 comprising:
(a) about 40 mol % of at least one constitutional repeating unit of the general formula selected from the group consisting of Formula I and Formula II; and
(b) about 60 mol % of at least one constitutional repeating unit of the general formula represented by Formula III.
47. The polymer or oligomer of claim 1 comprising:
(a) about 50 mol % of at least one constitutional repeating unit of the general formula selected from the group consisting of Formula I and Formula II; and
(b) about 50 mol % of at least one constitutional repeating unit of the general formula represented by Formula III.
48. The polymer of claim 1 wherein the polymer has an average molecular weight M w of at least about 15,000 Daltons.
49. The polymer of claim 1 wherein the polymer has a weight average molecular weight of at least about 20,000 Daltons.
50. The polymer of claim 1 wherein the polymer has a weight average molecular weight M w of at least about 40,000 Daltons.
51. The polymer of claim 1 wherein the polymer has a weight average molecular weight M w of at least about 60,000 Daltons.
52. The polymer of claim 1 wherein the polymer has a weight average molecular weight M w of at least about 80,000 Daltons.
53. The polymer of claim 1 wherein the polymer has a weight average molecular weight M w of at least about 100,000 Daltons.
54. The oligomer of claim 1 having a weight average molecular weight M w of from about 200 to about 15000 Daltons.
55. The polymer of claim 1 wherein the polymer is a copolymer.
56. The polymer of claim 55 wherein the polymer is a block co-polymer.
57. The polymer of claim 55 wherein the polymer is a random co-polymer.
58. The polymer of claim 1 wherein the polymer is a crosslinked polymer.
59. The polymer of claim 1 wherein the polymer is a hyperbranched polymer.
60. The polymer of claim 1 wherein the polymer is a star polymer.
61. The polymer of claim 1 wherein the polymer is a photoluminescent polymer and/or an electroluminescent polymer.
62. The photoluminescent polymer of claim 61 , wherein the photoluminescent polymer is suitable for excitation in the UV, visible, or infrared region.
63. The photoluminescent polymer of claim 61 , wherein the photoluminescent polymer is capable of emitting light having a wavelength in the range 350-750 nanometers.
64. The photoluminescent polymer of claim 61 , wherein the photoluminescent polymer is capable of emitting light having a wavelength in the range 450-700 nanometers.
65. The photoluminescent polymer of claim 61 , wherein the photoluminescent polymer is capable of emitting light having a wavelength in the range 500-650 nanometers.
66. A process of preparing a polymer or oligomer comprising:
(a) admixing
(i) at least one compound selected from the group consisting of Formula VIII, Formula IX, and Formula X, represented below
(ii) optionally, at least one compound of the general formula represented below by Formula XI:
wherein
R is H, D, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, 2-hydroxyphenyl, 2-alkoxyphenyl, 2-aryloxyphenyl, substituted 2-hydroxyphenyl, substituted 2-alkoxyphenyl, substituted 2-aryloxyphenyl, fluoroalkyl, or fluoroaryl;
A 5 is CH, CR 1 , or N;
A 6 is CH, CR 2 , or N;
A 7 is CH, CR 3 , or N;
A 8 is CH, CR 4 , or N;
R 1 , R 2 , R 3 , R 4 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and any two of adjacent R 1 , R 2 , R 3 or R 4 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran;
Q is selected from the group consisting of —Ar—, —O—, —S—, —NR 1 —, —OCR 1 R 2 —, —CR 1 R 2 —, —OCR 1 R 2 CR 3 R 4 —, —CR 1 R 2 CR 3 R 4 —, —N═CR 1 —, —CR 1 ═N—, —CR 1 ═CR 2 —, —N═N—, and —(CO)—, —BR 1 —, SiR 1 R 2 —, —(CO)—O—, —O—(CO)—, —NR 1 —(CO)—, and —(CO)—NR 1 —, C 3 to C 30 alkyldiyl, and C 3 to C 30 heteroalkyldiyl;
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl; and
R 6 and R 7 are optionally bridging;
Ar is unsubstituted or substituted, single or multiple ring, fused or non-fused aromatic or heteroaromatic; and
R 10 and R 10 ′ are each independently a group or groups capable of participating in aryl to aryl and/or aryl to alkyl coupling reaction; and
(b) adding a polymerization catalyst and optional co-reactants into the mixture to cause:
(i) polymerization to form a carbon to carbon bond linking at least one compound selected from the group consisting of Formula VIII, Formula IX, and Formula X with at least one other compound selected from the group consisting of Formula VIII, Formula IX, and Formula X; and/or
(ii) polymerization to form a carbon to carbon bond linking at least one compound selected from the group consisting of Formula VIII, Formula IX, and Formula X with at least one compound of Formula XI.
67. The process of claim 66 , wherein
R 10 and R 10 ′ are each independently a group or groups selected from the group consisting of H, D, halide, —Si(R 11 ), —Sn(R 11 ) 3 , —Cu, —Cu(CN)Li, —Li, —MgBr, —ZnCl, —ZnBr, —ZnI, —MnBr, —MnCl, —MnI, —HgCl, —OTf, —SH, —SO 3 CH 3 , —B(OR 12 ) 2 ;
R 11 is each independently selected from the group consisting of halide, hydroxyl, alkyl, and alkyloxy; and
R 12 is each independently selected from the group consisting of H, D, alkyl, and aryl or the two R 12 taken together with the oxygen atoms to which they are connected form cyclic boronic acid esters.
68. The process of claim 66 , wherein said aryl to aryl coupling reaction is selected from the group consisting of Suzuki, Colon, Stille, and Yamamoto.
69. The process of claim 66 , comprising admixing
(i) at least one compound of Formula XII represented below:
wherein
R is H, D, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, 2-hydroxyphenyl, 2-alkoxyphenyl, 2-aryloxyphenyl, substituted 2-hydroxyphenyl, substituted 2-alkoxyphenyl, substituted 2-aryloxyphenyl, fluoroalkyl, or fluoroaryl;
R 10 and R 10 ′ are each independently a group or groups capable of participating in aryl to aryl and/or aryl to alkyl coupling reaction; and
(ii) at least one compound of the general formula represented below by Formula XI:
wherein
Q is selected from the group consisting of —Ar—, —O—, —S—, —NR 1 —, —OCR 1 R 2 —, —CR 1 R 2 —, —OCR 1 R 2 CR 3 R 4 —, —CR 1 R 2 CR 3 R 4 —, —N═CR 1 —, —CR 1 ═N—, —CR 1 ═CR 2 —, —N═N—, and —(CO)—, —BR 1 —, SiR 1 R 2 —, —(CO)—O—, —O—(CO)—, —NR 1 —(CO)—, and —(CO)—NR 1 —, C 3 to C 30 alkyldiyl, and C 3 to C 30 heteroalkyldiyl;
R 1 , R 2 , R 3 , R 4 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and any two of adjacent R 1 , R 2 , R 3 or R 4 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
Ar is unsubstituted or substituted, single or multiple ring, fused or non-fused aromatic or hetero aromatic.
70. The process of claim 69 , wherein
R is
s is 0-5;
R 15 is selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and when s is 25, any two of adjacent R 15 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl and are optionally bridging.
71. The process of claim 70 , wherein
R is selected from the group consisting of:
R 50 and R 51 are each independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, fluoroalkyl, fluoroaryl, amide, and ester; and
R 52 is selected from the group consisting of alkyl, aryl, heteroaryl, fluoroalkyl, and fluoroaryl.
72. The process of claim 71 , wherein R is selected from the group consisting of:
73. The process of claim 69 , wherein R is alkyl.
74. The process of claim 73 , wherein R is n-hexyl.
75. The process of any of claims 69 - 74 , wherein R 10 and R 10 ′ in Formula X are each independently a halide.
76. The process of claim 75 , wherein R 10 and R 10 ′ in Formula X are each a bromide.
77. The process of any of claims 69 - 74 , wherein
R 10 and R 10 ′ in formula X are each independently
A 6 is CH, CR 2 , or N;
A 7 is CH, CR 3 , or N;
R 2 and R 3 are each independently selected from the group consisting of H, D, —NR 6 R 7 , halide, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, phenol, alkylphenol, fluoroalkyl, fluoroaryl, alkyleneoxy, polyalkylene oxy, polyalkylene, linear or dendritic; and R 2 and R 3 are optionally bridging, or taken together with the two carbons to which each is respectively attached may form an aromatic ring selected from the group consisting of unsubstituted or substituted benzene, naphthalene, anthracene, thiophene, pyridine, bipyridine, pyrazine, pyrimidine, oxadiazole, thiadiazole, and benzofuran; and
R 6 and R 7 are each independently substituted or unsubstituted alkyl or aryl and are optionally bridging.
78. The process of claim 77 , wherein R 10 and R 10 ′ in formula X are each
79. The process of claim 60 or 66 , comprising admixing
(i) at least one compound of Formula XI wherein
Q in Formula XI is
wherein
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging;
r is 0-4;
R 10 and R 10 ′ in formula XI are each independently —B(OR 12 ) 2 ;
R 12 is each independently selected from the group consisting of H, D, alkyl, and aryl, or the two R 12 taken together with the oxygen atoms to which they are connected form cyclic boronic acid esters; and/or
(ii) at least one other compound of Formula XI wherein
Q in Formula XI is selected from the group consisting of
R 5 is independently selected from the group consisting of H, D, F, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, linear, dendrimeric or hyperbranched polymeric, any two of adjacent R 5 groups are optionally bridging;
q is 0-3;
r is 0-4;
t is 0-6;
X is selected from the group consisting of —O—, —S—, —NR 6 —, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, —N═CR 6 —, —CR 6 ═CR 7 —, —N═N—, and —(CO)—;
Z is selected from the group consisting of —O—, —S—, —NR 6 —, aryl, alkoxy, aryloxy, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyl ketone, aryl ketone, alkylester, arylester, amide, carboxylic acid, fluoroalkyl, fluoroaryl, polyalkalene oxy, oxazole, oxadiazole, thiazole, thiadiazole, substituted triazole, tetrazole, tetrazine, triazine, substituted triazine, linear, dendrimeric or hyperbranched polymeric, and —CR 6 R 7 —, —CR 6 R 7 CR 8 R 9 —, N═CR 6 —, CR 6 ═CR 7 —, —N═N—, and —(CO)—;
R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of H, D, F, alkyl, alkaryl, heteroalkyl, aryl, aralkyl, heteroaryl, alkyleneoxy, polyalkylene oxy, alkoxy, aryloxy, fluoroalkyl, fluoroaryl, and linear or dendritic, and any two of adjacent R 6 , R 7 , R 8 , and R 9 are optionally bridging; and
R 10 and R 10 ′ in Formula XI are each independently a halide.
80. The process of claim 79 , wherein
in (i)
Q in Formula XI is selected from the group consisting of
R 10 and R 10 ′ in Formula XI are each independently —B(OR 12 ) 2 ;
R 12 is each independently selected from the group consisting of H, D, alkyl, and aryl, or the two R 12 taken together with the oxygen atoms to which they are connected form cyclic boronic acid esters; and
in (ii)
Q in Formula IX is selected from the group consisting of
R 10 and R 10 ′ in Formula XI are each independently a bromide.
81. The process of claim 79 , comprising admixing
(i) at least one said compound of Formula XI wherein
Q in Formula XI is
R 10 and R 10 ′ in Formula XI are each independently —B(OR 12 ) 2 ; and
R 12 is each independently selected from the group consisting of H, D, alkyl, and aryl, or the two R 12 taken together with the oxygen atoms to which they are connected form cyclic boronic acid esters.
82. The process of claim 81 , comprising further admixing
(i) at least one said compound of Formula XI wherein
Q in Formula XI is
R 10 and R 10 ′ are each a bromide.
83. The process of claim 66 , wherein said polymerization initiator is a palladium catalyst selected from the group consisting of Pd(PPh 3 ) 4 , Pd(OAc) 2 , PdCl 2 (dppb), and Pd(dba) 2 /PPh 3 , in combination with a base.
84. The process of claim 83 , wherein said base is selected from the group consisting of Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , KHCO 3 , CsOH, CsHCO 3 , Cs 2 CO 3 , Ba(OH) 2 , KOH, and NaOH.