Perylene semiconductors and methods of preparation and use thereof
View Patent ↗The present invention relates to semiconducting compounds, materials prepared from such compounds, methods of preparing such compounds and semiconductor materials, as well as various compositions, composites, and devices that incorporate the compounds and semiconductor materials. The semiconducting compounds can have higher electron-transport efficiency and higher solubility in common solvents compared to related representative compounds.
1. A compound of formula I:
wherein:
R 1 and R 2 , at each occurrence, independently are selected from a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 2-30 alkynyl group, a C 1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted with 1-4 groups independently selected from halogen, —CN, —NO 2 , —C(O)H, —C(O)OH, —CONH 2 , —OH, —NH 2 , —CO(C 1-10 alkyl), —C(O)OC 1-10 alkyl, —CONH(C 1-10 alkyl), —CON(C 1-10 alkyl) 2 , —S—C 1-10 alkyl, —O—(CH 2 CH 2 O) n (C 1-10 alkyl), —NH(C 1-10 alkyl), —N(C 1-10 alkyl) 2 , a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 2-10 alkynyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a C 6-14 aryl group, a C 3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group;
R 3 , R 4 , R 5 , and R 6 independently are H or CN, wherein at least one of R 3 , R 4 , R 5 , and R 6 is CN; and
n is 1, 2, 3, or 4.
2. The compound of claim 1 , wherein R 1 and R 2 , at each occurrence, are selected from a C 1-12 alkyl group, a C 1-12 haloalkyl group, and a phenyl group optionally substituted with 1-4 groups independently selected from a halogen, a C 1-6 alkyl group, and a C 1-6 haloalkyl group.
3. The compound of claim 1 , wherein R 1 , at each occurrence, is selected from a C 1-12 alkyl group and a phenyl group optionally substituted with a C 1-6 alkyl group; and R 2 , at each occurrence, is selected from a C 1-6 alkyl group and a C 1-6 haloalkyl group.
4. The compound of claim 1 , wherein each of R 1 and R 2 is selected from —CH 3 , —CF 3 , —C 2 H 5 , —C 3 H 7 , —C 4 H 9 , —C 5 H 11 , and a phenyl group optionally substituted with a C 1-6 alkyl group.
5. The compound of claim 1 , wherein each of R 3 and R 4 is —CN.
6. The compound of claim 1 , wherein each of R 3 and R 6 is —CN.
7. The compound of claim 1 , the compound having formula Ia or formula Ib:
wherein R 1 , R 2 , R 3 , R 4 , and R 6 are as defined in claim 1 .
8. The compound of claim 1 , the compound having the formula:
9. The compound of claim 1 , the compound having the formula:
10. The compound of claim 1 , the compound having the formula:
11. The compound of claim 1 , the compound having the formula:
12. The compound of claim 1 , the compound having the formula:
13. The compound of claim 1 , the compound having the formula:
14. The compound of claim 1 , the compound having the formula:
15. The compound of claim 1 , the compound having the formula:
16. The compound of claim 1 , the compound having the formula:
17. The compound of claim 1 , the compound having the formula:
18. A method of making the compound of claim 1 , said method comprising reacting a compound of formula II:
with a cyanide;
wherein
R 1 and R 2 , at each occurrence, independently are selected from H, a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 2-30 alkynyl group, a C 1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted with 1-4 groups independently selected from halogen, —CN, —NO 2 , —C(O)H, —C(O)OH, —CONH 2 , —OH, —NH 2 , —CO(C 1-10 alkyl), —C(O)OC 1-10 alkyl, —CONH(C 1-10 alkyl), —CON(C 1-10 alkyl) 2 , —S—C 1-10 alkyl, —O—(CH 2 CH 2 O) n (C 1-10 alkyl), —NH(C 1-10 alkyl), —N(C 1-10 alkyl) 2 , a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 2-10 alkynyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a C 6-14 aryl group, a C 3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group;
at least one of R 1 and at least one of R 2 , both of which are attached to a common carbon atom, are independently selected from a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 2-30 alkynyl group, a C 1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted as described herein;
X, at each occurrence, is H or a halogen; and
n is 1, 2, 3, or 4.
19. The method of claim 18 , wherein the cyanide is CuCN.
20. The method of claim 18 , wherein the reaction is conducted at an elevated temperature.
21. The method of claim 20 , wherein the elevated temperature is about 70° C. or about 150° C.
22. The method of claim 18 , wherein the compound of formula II is prepared by reacting a compound of formula III:
with an amine in an aprotic solvent, wherein X, at each occurrence, is H or a halogen.
23. The method of claim 22 , wherein the amine is
wherein R 1 and R 2 , at each occurrence, independently are selected from H, a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 2-30 alkynyl group, a C 1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted with 1-4 groups independently selected from halogen, —CN, —NO 2 , —C(O)H, —C(O)OH, —CONH 2 , —OH, —NH 2 , —CO(C 1-10 alkyl), —C(O)OC 1-10 alkyl, —CONH(C 1-10 alkyl), —CON(C 1-10 alkyl) 2 , —S—C 1-10 alkyl, —O—(CH 2 CH 2 O) n (C 1-10 NH(C 1-10 alkyl), —N(C 1-10 alkyl) 2 , a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 2-10 alkynyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a C 6-14 aryl group, a C 3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group; and n is 1, 2, 3, or 4.
24. The method of claim 22 , wherein the aprotic solvent is (C 1-6 alkyl)O(CH 2 CH 2 O) m (C 1-6 alkyl), and m is selected from 1, 2, 3, 4, 5, and 6.
25. The method of claim 22 , wherein the aprotic solvent is triethylene glycol dimethyl ether.
26. The method of claim 18 , wherein X, at each occurrence, is H or Br.
27. The method of claim 18 , wherein the compound of formula II is selected from:
28. A composition comprising one or more compounds according to claim 1 dissolved or dispersed in a liquid medium.
29. The composition of claim 28 , wherein the composition comprises two or more regioisomers of the one or more compounds according to claim 1 .
30. The composition of claim 28 , wherein the liquid medium is an organic solvent or a mixture of solvents.
31. An article of manufacture comprising one or more compounds according to claim 1 .
32. The article of manufacture of claim 31 , wherein the article of manufacture comprises two or more regioisomers of the compounds according to claim 1 .
33. The article of manufacture of claim 31 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device.
34. A thin film semiconductor comprising one or more compounds according to claim 1 .
35. The thin film semiconductor of claim 34 , wherein the thin film semiconductor comprises two or more regioisomers of a compound of formula I:
wherein:
R 1 and R 2 , at each occurrence, independently are selected from a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 2-30 alkynyl group, a C 1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted with 1-4 groups independently selected from halogen, —CN, —NO 2 , —C(O)H, —C(O)OH, —CONH 2 , —OH, —NH 2 , —CO(C 1-10 alkyl), —C(O)OC 1-10 alkyl, —CONH(C 1-10 alkyl), —CON(C 1-10 alkyl) 2 , —S—C 1-10 alkyl, —O—(CH 2 CH 2 O) n (C 1-10 alkyl), —NH(C 1-10 alkyl), —N(C 1-10 alkyl) 2 , a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 2-10 alkynyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a C 6-14 aryl group, a C 3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group;
R 3 , R 4 , R 5 , and R 6 independently are H or CN, wherein at least one of R 3 , R 4 , R 5 , and R 6 is CN; and
n is 1, 2, 3, or 4.
36. A composite comprising a substrate and the thin film semiconductor of claim 34 deposited on the substrate.
37. A field effect transistor device comprising the thin film semiconductor of claim 34 .
38. A field effect transistor device comprising the composite of claim 36 .
39. The field effect transistor device of claim 37 comprising a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material.
40. A photovoltaic device comprising the thin film semiconductor of claim 34 .
41. A photovoltaic device comprising the composite of claim 36 .
42. The photovoltaic device of claim 40 comprising a p-type semiconducting material adjacent to the thin film semiconductor.
43. An organic light emitting diode device comprising the thin film semiconductor of claim 34 .
44. An organic light emitting diode device comprising the composite of claim 36 .
45. A unipolar or complementary circuit device comprising the thin film semiconductor of claim 34 .
46. A unipolar or complementary circuit device comprising the composite of claim 36 .
47. A method of making an article of manufacture of claim 31 , said method comprising depositing a composition comprising one or more compounds of formula I dissolved or dispersed in a liquid medium, said one or more compounds of formula I being:
wherein:
R 1 and R 2 , at each occurrence, independently are selected from a C 1-30 alkyl group, a C 2-30 alkenyl group, a C 2-30 alkynyl group, a C 1-30 haloalkyl group, and a 3-22 membered cyclic moiety, each optionally substituted with 1-4 groups independently selected from halogen, —CN, —NO 2 , —C(O)H, —C(O)OH, —CONH 2 , —OH, —NH 2 , —CO(C 1-10 alkyl), —C(O)OC 1-10 alkyl, —CONH(C 1-10 alkyl), —CON(C 1-10 alkyl) 2 , —S—C 1-10 alkyl, —O—(CH 2 CH 2 O) n (C 1-10 alkyl), —NH(C 1-10 alkyl), —N(C 1-10 alkyl) 2 , a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 2-10 alkynyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a C 6-14 aryl group, a C 3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group;
R 3 , R 4 , R 5 , and R 6 independently are H or CN, wherein at least one of R 3 , R 4 , R 5 , and R 6 is CN; and
n is 1, 2, 3, or 4.
48. The method of claim 47 , wherein depositing the composition comprises at least one of vacuum vapor deposition, printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying.
49. A compound having the formula:
50. A compound having the formula:
51. A compound having the formula:
52. A compound having the formula:
53. A compound having the formula:
54. A compound having the formula:
55. A compound having the formula:
56. A compound having the formula:
57. A compound having the formula: