Semiconducting co-polymers of methylenedihydropyrazines with fused thiophenes

1. A composition, comprising a dialkoxydimethylenedihydropyrazine (AMDHP) fused-thiophene (FT) organic semiconductor polymer having a repeat unit of Formula 2 or Formula 3, or a salt or isomer thereof:

wherein m is an integer greater than or equal to zero;

wherein n is an integer greater than or equal to one;

X and Y are, independently, a covalent bond or aryl;

A and B are, independently, a nitrogen group or a C—H group;

R 1 and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted;

R 3 and R 4 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted; and

p and q are, independently, integers greater than or equal to zero.

2. The composition of claim 1 , wherein A and B are nitrogen.

3. The composition of claim 1 , wherein at least one of R 1 and R 2 comprises a substituted or unsubstituted alkyl.

4. The composition of claim 3 , wherein at least one of R 1 and R 2 comprises an unsubstituted alkyl.

5. The composition of claim 1 , wherein at least one of R 3 and R 4 comprises a substituted or unsubstituted alkyl.

6. The composition of claim 5 , wherein at least one of R 3 and R 4 comprises a substituted or unsubstituted alkyl group comprising at least six carbon atoms.

7. The composition of claim 1 , wherein X and Y are, independently, at least one unfused thiophene groups.

8. The composition of claim 1 , wherein p and q are different values.

9. A polymer comprising the composition of claim 1 , wherein the polymer has a molecular weight in a range of 4000 Da to 180,000 Da.

10. An organic thin film transistor (OTFT) comprising:

a substrate;

a gate electrode;

a gate dielectric layer;

a patterned source and drain layer; and

an organic semiconductor layer, wherein the organic semiconductor layer comprises a polymer having the composition of claim 1 .

11. A device comprising the composition of claim 1 configured in an electronic, optoelectronic, or nonlinear optical device.

12. The device of claim 11 , wherein the device comprises a transistor (FET), a thin-film transistor (TFT), an organic light-emitting diode (OLED), an electro-optic (EO) device, a conductive material, a two photon mixing material, an organic semiconductor, a RFID tag, an electroluminescent device, or a photovoltaic and sensor device.

13. A composition having a repeat unit of Formula 4, or a salt or isomer thereof:

wherein n is an integer greater than one.

14. A method of fabricating a dialkoxydimethylenedihydropyrazine (AMDHP) fused-thiophene (FT) organic semiconductor polymer, comprising:

reacting tin-substituted dialkylated tetrathienoacene or thienyl-dialkylated tetrathienoacene with halogen-substituted thienyl-AMDHP; or

reacting halogen-substituted dialkylated tetrathienoacene or thienyl-dialkylated tetrathienoacene with tin-substituted thienyl-AMDHP.

15. The method of claim 14 , wherein the halogen-substituted dialkylated tetrathienoacene comprises:

or a salt or isomer thereof,

wherein H 1 and H 2 are, independently, chlorine (Cl), bromine (Br), and iodine (I), and

wherein R 1 and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

16. The method of claim 15 , wherein at least one of H 1 and H 2 are Br.

17. The method of claim 14 , wherein the tin-substituted dialkylated tetrathienoacene comprises:

or a salt or isomer thereof,

wherein R 1 , R 2 , R 5 , and R 6 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

18. The method of claim 17 , wherein at least one of R 5 and R 6 are substituted or unsubstituted alkyl groups.

19. The method of claim 14 , wherein the thienyl-dialkylated tetrathienoacene comprises:

or a salt or isomer thereof,

wherein R 1 and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

20. The method of claim 14 , wherein the halogen-substituted thienyl-AMDHP comprises:

or a salt or isomer thereof,

wherein H 3 and H 4 are, independently, chlorine (Cl), bromine (Br), and iodine (I), and

wherein R 3 and R 4 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

21. The method of claim 20 , wherein at least one of H 3 and H 4 are Br.

22. The method of claim 14 , wherein the tin-substituted thienyl-AMDHP comprises:

or a salt or isomer thereof,

wherein R 3 , R 4 , R 7 , and R 8 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, vinyl ether, or combinations thereof, with each of the preceding being substituted or unsubstituted.

23. The method of claim 22 , wherein at least one of R 7 and R 8 are substituted or unsubstituted alkyl groups.