Thienocoronene-imide semiconducting compounds and polymers
View Patent ↗Disclosed are new semiconductor materials prepared from thienocoronene-imide-based small molecule and/or polymeric compounds. Such compounds can exhibit high carrier mobility and/or good current modulation characteristics. In addition, the compounds of the present teachings can possess certain processing advantages such as solution-processability and/or good stability at ambient conditions.
1. A polymer comprising identical or different repeating units having the formula:
or both,
wherein:
R 1 and R 2 independently are selected from H, a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 1-40 haloalkyl group, -L′-Cy 1 , -L′-Cy 1 -L′-Cy 2 , -L′-Cy 1 -L′-Cy 2 —Cy 2 , -L′-Cy 1 —Cy 1 , -L′-Cy 1 —Cy 1 -L′-Cy 2 , -L′-Cy 1 —Cy 1 -L′-Cy 2 —Cy 2 , -L′-Cy 1 -L-R, -L′-Cy 1 -L′-Cy 2 -L-R, -L′-Cy 1 -L′-Cy 2 —Cy 2 -L-R, -L′-Cy 1 —Cy 1 -L-R, and -L′-Cy 1 —Cy 1 -L′-Cy 2 -L-R,
wherein:
each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group optionally is substituted with 1-10 substituents independently selected from a halogen,
—CN, NO 2 , OH, —NH 2 , —NH(C 1-40 alkyl), —N(C 1-40 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-40 alkyl, —C(O)OH, —C(O)—OC 1-40 alkyl, —C(O)NH 2 , —C(O)NH—C 1-40 alkyl, —C(O)N(C 1-40 alkyl) 2 , —OC 1-40 alkyl, —SiH 3 , —SiH(C 1-40 alkyl) 2 , —SiH 2 (C 1-40 alkyl), and —Si(C 1-40 alkyl) 3 ;
each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group can be bonded covalently to the imide nitrogen atom via an optional linker;
R is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, and a C 1-40 haloalkyl group, each of which optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-40 alkyl), —N(C 1-40 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-40 alkyl, —C(O)OH, —C(O)—OC 1-40 alkyl, —C(O)NH 2 , —C(O)NH—C 1-40 alkyl, —C(O)N(C 1-40 alkyl) 2 , —OC 1-40 alkyl, —SiH 3 , —SiH(C 1-40 alkyl) 2 , —SiH 2 (C 1-40 alkyl), and —Si(C 1-40 alkyl) 3 ;
Cy 1 and Cy 2 independently are selected from a C 6-14 aryl group, a 5-14 membered heteroaryl group, a C 3-14 cycloalkyl group, and a 3-14 membered cycloheteroalkyl group, each of which optionally is substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;
L is a covalent bond or a linker selected from —Y—O—Y—, —Y—[S(O) w ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —Y—, and —Y—[SiR c 2 ]—Y—;
L′, at each occurrence, independently is a covalent bond or a linker selected from —Y—O—Y—, —Y—[S(O) w ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —Y—, —Y—[SiR c 2 ]—Y—, a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, and a divalent C 1-40 haloalkyl group,
wherein:
Y, at each occurrence, independently is selected from a divalent C 1-40 alkyl group, divalent C 2-40 alkenyl group, a divalent C 1-40 haloalkyl group, and a covalent bond;
R c is selected from H, a C 1-6 alkyl group, a C 6-14 aryl group, and a —C 1-6 alkyl-C 6-14 aryl group; and
w is 0, 1, or 2;
wherein the polymer has a degree of polymerization (n) that is greater than 2.
2. The polymer of claim 1 , wherein the polymer is a homopolymer consisting of repeating units having the formula:
wherein R 1 and R 2 are as defined in claim 1 .
3. A copolymer represented by the formula:
wherein:
M 1 has the formula:
M 2 has a formula selected from:
wherein:
R 1 and R 2 independently are selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, and a C 1-40 haloalkyl group, wherein:
each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group optionally is substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-40 alkyl), —N(C 1-40 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-40 alkyl, —C(O)OH, —C(O)—OC 1-40 alkyl, —C(O)NH 2 , —C(O)NH—C 1-40 alkyl, —C(O)N(C 1-40 alkyl) 2 , —OC 1-40 alkyl, —SiH 3 , —SiH(C 1-40 alkyl) 2 , —SiH 2 (C 1-40 alkyl), and —Si(C 1-40 alkyl) 3 ; and
each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group can be bonded covalently to the imide nitrogen atom via an optional linker;
π-2, at each occurrence, independently is an optionally substituted fused ring moiety;
Ar, at each occurrence, independently is an optionally substituted monocyclic moiety;
Z, at each occurrence, independently is a conjugated linear linker;
m, at each occurrence, is 1, 2, 3, 4, 5 or 6;
m′ and m″, at each occurrence, independently are 0, 1, 2, 3, 4, 5 or 6;
n is an integer in the range of 2 to 10,000; and
x and y represent the molar fraction of M 1 and the molar fraction of M 2 , respectively.
4. The polymer of claim 3 having formula III, IV, V, VI, VII, or VIII:
wherein R 1 , R 2 , Ar, π-2, Z, m and n are as defined in claim 3 .
5. The polymer according to claim 3 , wherein M 2 is
and is selected from:
wherein R 5 and R 6 , at each occurrence, independently are selected from H, a halogen, —CN, a C 1-40 alkyl group, and a C 1-30 haloalkyl group.
6. The polymer according to claim 3 , wherein M 2 is
wherein π-2 is selected from:
wherein R 7 is selected from H, a halogen, —CN, a C 1-40 alkyl group, and a C 1-40 haloalkyl group, and Ar, m′, and m″ are as defined in claim 3 .
7. The polymer according to claim 6 , wherein m′ and m″ are 0.
8. The polymer according to claim 3 , wherein M 2 is
and is selected from:
wherein R 5 , at each occurrence, independently is selected from H, a halogen, —CN, a C 1-40 alkyl group, and a C 1-40 haloalkyl group; R 7 is selected from H, a C 1-40 alkyl group, and a C 1-40 haloalkyl group; and R c is selected from H, a C 1-6 alkyl group, and a —C 1-6 alkyl-C 6-14 aryl group.
9. A polymer selected from:
wherein n is an integer in the range of 2 to 10,000.
10. A thin film semiconductor comprising one or more polymers of claim 1 .
11. An electronic, optical, or optoelectronic device comprising the thin film semiconductor of claim 10 .
12. The polymer of claim 1 , wherein R 1 and R 2 independently are a linear or branched C 1-40 alkyl or haloalkyl group.
13. The polymer of claim 3 , wherein R 1 and R 2 independently are a linear or branched C 1-40 alkyl or haloalkyl group.
14. A thin film semiconductor comprising one or more polymers of claim 3 .
15. An electronic, optical, or optoelectronic device comprising the thin film semiconductor of claim 14 .
16. A thin film semiconductor comprising one or more polymers of claim 9 .
17. An electronic, optical, or optoelectronic device comprising the thin film semiconductor of claim 16 .