Azinothiadiazole compounds and related semiconductor devices

1. A semiconducting compound, the semiconducting compound being a polymer having a first repeating unit M 1 comprising one or more divalent azino[1,2,3]thiadiazole moieties represented by formula (I):

wherein:

each W independently is selected from the group consisting of N, CH, and CR 1 , provided that at least one of the W is N; and

R 1 is selected from the group consisting of halogen, —CN, NO 2 , R 2 , -L-R 3 , OH, OR 2 , OR 3 , NH 2 , NHR 2 , N(R 2 ) 2 , NR 2 R 3 , N(R 3 ) 2 , SH, SR 2 , SR 3 , S(O) 2 OH, —S(O) 2 OR 2 , —S(O) 2 OR 3 , C(O)H, C(O)R 2 , C(O)R 3 , C(O)OH, C(O)OR 2 , C(O)OR 3 , C(O)NH 2 , C(O)NHR 2 , C(O)N(R 2 ) 2 , C(O)NR 2 R 3 , C(O)N(R 3 ) 2 , SiH 3 , SiH(R 2 ) 2 , SiH 2 (R 2 ), and Si(R 2 ) 3 , wherein L is selected from the group consisting of a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, a divalent C 1-40 haloalkyl group, and a covalent bond; R 2 is selected from the group consisting of a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and R 3 is selected from the group consisting of a C 3-10 cycloalkyl group, a C 6-14 aryl group, a C 6-14 haloaryl group, a 3-12 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group, each of which optionally is substituted with 1-5 substituents independently selected from the group consisting of halogen, —CN, NO 2 , R 2 , OR 2 , and SR 2 ,

wherein said polymer has a degree of polymerization (n) ranging from 3 to 1,000.

2. The compound of claim 1 , wherein R 1 is selected from the group consisting of F, Cl, —CN, —NO 2 , R 2 , OR 2 , and SR 2 , wherein R 2 is selected from the group consisting of a linear or branched C 1-40 alkyl group, a linear or branched C 2-40 alkenyl group, and a linear or branched C 1-40 haloalkyl group.

3. The compound of claim 1 , wherein one of the W is N and the other W is CR 1 , wherein R 1 is selected from the group consisting of F, Cl, and a C 1-40 alkyl group.

4. The compound of claim 1 , wherein one of the W is N and the other W is selected from the group consisting of N, CH, CF, and CCl.

5. The compound of claim 1 , wherein M 1 is selected from the group consisting of:

wherein:

pi-2 is an optionally substituted C 8-26 aryl group or 8-26 membered heteroaryl group;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

6. The compound of claim 5 , wherein pi-2 is selected from the group consisting of:

wherein:

R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

R b is selected from the group consisting of H, R, and -L-R f ;

R c is H or R;

R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L-R f ;

R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and R f ;

R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and

R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group.

7. The compound of claim 5 , wherein Ar in (Ar) m and (Ar) m′ is represented by:

wherein each X independently is selected from the group consisting of N, CH, and CR 4 , wherein R 4 is selected from the group consisting of F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 is selected from the group consisting of a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group.

8. The compound of claim 7 , wherein (Ar) m and (Ar) m′ independently are selected from the group consisting of:

wherein R 4 , at each occurrence, independently is selected from the group consisting of F, Cl, CN, R 2 , OR 2 , and SR 2 , where R 2 is a linear or branched C 1-40 alkyl or haloalkyl group.

9. The compound of claim 5 , wherein Z is selected from the group consisting of:

wherein R 4 is selected from the group consisting of F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 is selected from the group consisting of a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group.

10. The compound of claim 5 , further comprising one or more repeating units other than M 1 , the one or more other repeating units (M 2 ) being selected from the group consisting of:

wherein:

pi-2 is an optionally substituted conjugated polycyclic moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;

m″ is 1, 2, 3, 4, 5 or 6; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

11. The compound of claim 10 , wherein in the one or more M 2 repeating units, Z is selected from the group consisting of:

(Ar) m , (Ar) m′ , and (Ar) m″ independently are selected from the group consisting of:

wherein R 4 is selected from F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and

pi-2 is selected from the group consisting of:

wherein:

R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

R b is selected from the group consisting of H, R, and -L-R f ;

R c is H or R;

R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L-R f ; and

R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and R f ; wherein

R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group; and

R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group.

12. The compound of claim 11 , wherein M 1 is selected from the group consisting of:

wherein R 4 is selected from the group consisting of R 2 , OR 2 , and SR 2 , where R 2 is a linear or branched C 1-40 alkyl or haloalkyl group; and

M 2 is selected from the group consisting of:

wherein (Ar) m and (Ar) m′ are selected from the group consisting of:

13. The compound of claim 12 , wherein the compound is a random copolymer having a formula selected from the group consisting of:

wherein M 1A and M 1B represent different repeating units M 1 , and M 2A and M 2B represent different repeating units M 2 , x and y are real numbers representing molar ratios, and n is the degree of polymerization.

14. An electronic, optical or optoelectronic device comprising a semiconductor component, the semiconductor component comprising a compound of claim 1 .

15. An organic photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, optionally one or more cathode interlayers, and in between the anode and the cathode a semiconductor component comprising a blend material, the blend material comprising an electron-acceptor compound and an electron-donor compound, the electron-donor compound being a compound of claim 1 .

16. An organic thin film transistor comprising a substrate, a thin film semiconductor, a dielectric layer, a gate electrode, and source and drain electrodes, wherein the thin film semiconductor comprises a compound of claim 1 .

17. A semiconducting compound wherein the compound is a small molecule represented by a formula selected from the group consisting of:

wherein:

each W independently is selected from the group consisting of N, CH, and CR 1 , provided that at least one of the W is N; and

R 1 is selected from the group consisting of halogen, —CN, NO 2 , R 2 , -L-R 3 , OH, OR 2 , OR 3 , NH 2 , NHR 2 , N(R 2 ) 2 , NR 2 R 3 , N(R 3 ) 2 , SH, SR 2 , SR 3 , S(O) 2 OH, —S(O) 2 OR 2 , —S(O) 2 OR 3 , C(O)H, C(O)R 2 , C(O)R 3 , C(O)OH, C(O)OR 2 , C(O)OR 3 , C(O)NH 2 , C(O)NHR 2 , C(O)N(R 2 ) 2 , C(O)NR 2 R 3 , C(O)N(R 3 ) 2 , SiH 3 , SiH(R 2 ) 2 , SiH 2 (R 2 ), and Si(R 2 ) 3 , wherein L is selected from the group consisting of a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, a divalent C 1-40 haloalkyl group, and a covalent bond; R 2 is selected from the group consisting of a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and R 3 is selected from the group consisting of a C 3-10 cycloalkyl group, a C 6-14 aryl group, a C 6-14 haloaryl group, a 3-12 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group, each of which optionally is substituted with 1-5 substituents independently selected from the group consisting of halogen, —CN, NO 2 , R 2 , OR 2 , and SR 2 ;

Q 1 and Q 2 independently are selected from the group consisting of H, R 2 , and C(O)R 2 , wherein R 2 is a C 1-40 alkyl or haloalkyl group;

pi-2 is an optionally substituted conjugated polycyclic moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;

m″ is 1, 2, 3, 4, 5 or 6; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

18. The compound of claim 17 , wherein the compound is represented by a formula selected from the group consisting of:

19. The compound of claim 18 selected from the group consisting of:

20. An electronic, optical or optoelectronic device comprising a semiconductor component, the semiconductor component comprising a semiconducting compound comprising one or more azino[1,2,3]thiadiazole moieties represented by formula (I):

wherein:

each W independently is selected from the group consisting of N and CR 1 , provided that at least one of the W is N; and

R 1 is selected from the group consisting of F, Cl, —CN, —NO 2 , R 2 , OR 2 , and SR 2 , wherein R 2 is selected from the group consisting of a linear or branched C 1-40 alkyl group, a linear or branched C 2-40 alkenyl group, and a linear or branched C 1-40 haloalkyl group.

21. The device of claim 20 , wherein one of the W is N and the other is CR.

22. The device of claim 20 , wherein the device is an organic photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, optionally one or more cathode interlayers, and in between the anode and the cathode a semiconductor component comprising a blend material, the blend material comprising an electron-acceptor compound and an electron-donor compound, the electron-donor compound being the semiconducting compound comprising one or more azino[1,2,3]thiadiazole moieties represented by formula (I).

23. The device of claim 20 , wherein the device is an organic thin film transistor comprising a substrate, a thin film semiconductor, a dielectric layer, a gate electrode, and source and drain electrodes, wherein the thin film semiconductor comprises the semiconducting compound comprising one or more azino[1,2,3]thiadiazole moieties represented by formula (I).

24. An electronic, optical or optoelectronic device comprising a semiconductor component, the semiconductor component comprising a semiconducting compound comprising one or more azino[1,2,3]thiadiazole moieties represented by formula (I):

wherein:

each W independently is selected from the group consisting of N, CH, and CR 1 , provided that at least one of the W is N; and

R 1 is selected from the group consisting of halogen, —CN, NO 2 , -L-R 3 , OH, OR 2 , OR 3 , NH 2 , NHR 2 , N(R 2 ) 2 , NR 2 R 3 , N(R 3 ) 2 , SH, SR 2 , SR 3 , S(O) 2 OH, —S(O) 2 OR 2 , —S(O) 2 OR 3 , C(O)H, C(O)R 2 , C(O)R 3 , C(O)OH, C(O)OR 2 , C(O)OR 3 , C(O)NH 2 , C(O)NHR 2 , C(O)N(R 2 ) 2 , C(O)NR 2 R 3 , C(O)N(R 3 ) 2 , SiH 3 , SiH(R 2 ) 2 , SiH 2 (R 2 ), and Si(R 2 ) 3 , wherein L is selected from the group consisting of a divalent C 1-40 alkyl group, a divalent C 2-40 alkenyl group, a divalent C 1-40 haloalkyl group, and a covalent bond; R 2 is selected from the group consisting of a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and R 3 is selected from the group consisting of a C 3-10 cycloalkyl group, a C 6-14 aryl group, a C 6-14 haloaryl group, a 3-12 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group, each of which optionally is substituted with 1-5 substituents independently selected from the group consisting of halogen, —CN, NO 2 , R 2 , OR 2 , and SR 2 .

25. The device according to claim 24 , that is an organic photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, optionally one or more cathode interlayers, and in between the anode and the cathode a semiconductor component comprising a blend material, the blend material comprising an electron-acceptor compound and an electron-donor compound, the electron-donor compound being the semiconducting compound comprising one or more azino[1,2,3]thiadiazole moieties represented by formula (I).

26. The device according to claim 24 , that is an organic thin film transistor comprising a substrate, a thin film semiconductor, a dielectric layer, a gate electrode, and source and drain electrodes, wherein the thin film semiconductor comprises the semiconducting compound comprising one or more azino[1,2,3]thiadiazole moieties represented by formula (I).