Functionnalized benzodithiophene polymers for electronic application

1. A polymer, comprising a repeating unit of the formula

wherein

R 1 is hydrogen, C 1 -C 100 alkyl, or a group of formula —SiR 501 R 502 R 503 ;

R 2 is —CN, —CF 3 , a fluorine atom, or a group of the formula

R 301 , R 302 and R 303 are independently of each other C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E′ and/or interrupted by D′, C 1 -C 100 fluoroalkyl, C 3 -C 12 cycloalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl group, which is be substituted by G′; C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 7 -C 25 aralkyl, or C 7 -C 25 aralkyl which is substituted by G′; C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl, which is substituted by G′;

R 601 and R 602 are independently of each other H, or C 1 -C 25 alkyl;

R 501 , R 502 and R 503 are independently of each other C 1 -C 8 alkyl, C 6 -C 24 aryl, or C 7 -C 12 aralkyl;

D′ is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, —NR 65 —, —SiR 70 R 71 —, —POR 72 —, —CR 63 ═CR 64 —, or —C≡C—, and

E′ is —OR 69 , —SR 69 , —NR 65 R 66 , —COR 68 , —COOR 67 , —CONR 65 R 66 , —CN, CF 3 , or halogen,

G′ is E′, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O—,

R 63 and R 64 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—;

R 65 and R 66 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—; or

R 65 and R 66 together form a five or six membered ring,

R 67 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl;

or C 1 -C 18 alkyl which is interrupted by —O—,

R 68 is H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,

R 69 is C 6 -C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,

R 70 and R 71 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and

R 72 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl.

2. The polymer according to claim 1 , which is a polymer comprising a repeating unit of the formula

wherein

R 1 is hydrogen, or C 1 -C 100 alkyl,

R 301 is C 1 -C 18 alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C 1 -C 18 alkyl, halogen, OR 69 , CN, or CF 3 ; wherein R 69 is C 1 -C 18 alkyl, or phenyl;

R 601 and R 602 are the same and are hydrogen or C 1 -C 18 alkyl.

3. The polymer according to claim 1 , which is a polymer comprising a repeating unit of the formula

wherein

R 1 is hydrogen, or C 1 -C 100 alkyl, and

R 601 and R 602 are the same and are hydrogen, or C 1 -C 18 alkyl.

4. The polymer according to claim 1 , wherein the polymer is a polymer of formula

or a polymer, comprising repeating units of the formula

wherein

n is in the range of 4 to 1000,

A is a repeating unit of formula (I), and

—COM1- is a repeating unit

wherein

k is 0, 1, 2, or 3; 1 is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3;

Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a group of formula and

wherein

X is —O—, —S—, —NR 8 —, —Si(R 11 )(R 11′ )—, —Ge(R 11 )(R 11′ )—, —C(R 7 )(R 7′ )—, —C(═O)—,

wherein

X 1′ is S, O, NR 107 —, —Si(R 117 )(R 117′ )—, —Ge(R 117 )(R 117′ )—, —C(R 108 )(R 109 )—, —C(═O)—,

R 3 and R 3′ are independently of each other hydrogen, halogen, halogenated C 1 -C 25 alkyl, cyano, C 1 -C 25 alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 104 and R 104′ are independently of each other hydrogen, cyano, COOR 103 , a C 1 -C 25 alkyl group, or C 6 -C 24 aryl or C 2 -C 20 heteroaryl,

R 4 , R 4′ , R 5 , R 5′ , R 6 , and R 6′ are independently of each other hydrogen, halogen, halogenated C 1 -C 25 alkyl, cyano, C 1 -C 25 alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 25 arylalkyl,

R 8 and R 8′ are independently of each other hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 arylalkyl,

R 11 and R 11′ are independently of each other C 1 -C 25 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, which are optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;

R 12 and R 12′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 2 -C 25 arylalkyl, or

wherein R 13 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)alkyl group;

R 104 and R 104′ are independently of each other hydrogen, C 1 -C 18 alkyl, C 6 -C 10 aryl, which are optionally substituted by G, or C 2 -C 8 heteroaryl, which is optionally substituted by G,

R 105 , R 105′ , R 106 and R 106′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 18 alkoxy,

R 107 is hydrogen, C 7 -C 25 arylalkyl, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 perfluoroalkyl; C 1 -C 25 alkyl; which is optionally interrupted by —O—, or —S—; or —COOR 103 ;

R 108 and R 109 are independently of each other H, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or C 7 -C 25 aralkyl, or

R 108 and R 109 together form a group of formula ═CR 100 R 111 , wherein

R 110 and R 111 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, or C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G, or

R 108 and R 109 together form a five or six membered ring, which optionally can be substituted by C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or C 7 -C 25 aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR 112′ —,

E is C 1 -C 8 thioalkoxy, C 1 -C 8 alkoxy, CN, —NR 112′ R 113′ , —CONR 112′ R 113′ , or halogen,

G is E, or C 1 -C 18 alkyl, and

R 112′ and R 113′ are independently of each other H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,

R 115 and R 115′ are independently of each other hydrogen, halogen, cyano, C 1 -C 25 alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or

wherein R 116 is a C 1 -C 18 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group;

R 117 and R 117′ are independently of each other C 1 -C 25 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, which are optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;

R 118 , R 119 , R 120 and R 121 are independently of each other hydrogen, halogen, halogenated C 1 -C 25 alkyl, cyano, C 1 -C 25 alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 122 and R 122′ are independently of each other hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 arylalkyl;

R 201 is selected from hydrogen, a C 1 -C 100 alkyl group, —COOR 103 , a C 1 -C 100 alkyl group substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C 6 -C 18 aryl groups and/or interrupted by —O—, —COO—, —OCO— or —S—; a C 7 -C 25 arylalkyl group, a carbamoyl group, a C 5 -C 12 cycloalkyl group, which are substituted one to three times with C 1 -C 100 alkyl and/or C 1 -C 100 alkoxy, a C 6 -C 24 aryl group, which are optionally substituted one to three times with C 1 -C 100 alkyl, C 1 -C 100 thioalkoxy, and/or C 1 -C 100 alkoxy; and pentafluorophenyl;

R 103 and R 114 are independently of each other C 1 -C 25 alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms,

R 202 and R 203 may be the same or different and are selected from H, F, —CN, C 1 -C 100 alkyl, which are optionally interrupted by one or more oxygen, or sulphur atoms; and C 1 -C 100 alkoxy.

5. The polymer according to claim 1 , comprising repeating units of the formula

wherein

A is a repeating unit of formula (I), and

COM 1 - is a repeating unit of formula

wherein

R 3 , R 3′ , R 4 and R 4′ are independently of each other hydrogen, or C 1 -C 25 alkyl;

R 8 and R 8′ are independently of each other hydrogen, or C 1 -C 25 alkyl;

R 114 is a C 1 -C 38 alkyl group;

R 201 is a C 1 -C 38 alkyl group; and

R 202 and R 203 are independently of each other hydrogen or C 1 -C 25 alkyl.

6. The polymer according to claim 4 , which is a polymer of formula

wherein n is 4 to 1000,

A is a repeating unit of formula

wherein R 1 is selected from hydrogen, or C 1 -C 25 alkyl,

R 301 is C 1 -C 18 alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C 1 -C 18 alkyl, halogen, OR 69 , CN, or CF 3 ; wherein R 69 is C 1 -C 18 alkyl, or phenyl;

R 601 and R 602 are hydrogen; and

is a group of formula

wherein R 3 , R 3′ , R 4 and R 4′ are independently of each other hydrogen, or C 1 -C 25 alkyl; and

R 201 is a C 1 -C 38 alkyl group.

7. The polymer according to claim 5 , which is a polymer of the formula

wherein

n is 4 to 1000;

R 1 is hydrogen or C 1 -C 100 alkyl,

R 3 and R 3′ are independently of each other hydrogen or C 1 -C 25 alkyl;

R 201 is a C 1 -C 38 alkyl group,

R 301 is C 1 -C 18 alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C 1 -C 18 alkyl, halogen, OR 69 , CN, or CF 3 ; wherein R 69 is C 1 -C 18 alkyl, or phenyl;

R 601 and R 602 are independently of each other hydrogen, or C 1 -C 25 alkyl.

8. An organic semiconductor material, layer or component, comprising the polymer according to claim 1 .

9. An electronic device, comprising the polymer according to claim 1 .

10. The electronic device according to claim 9 , wherein the electronic device is an organic light emitting diode, an organic photovoltaic device, a photodiode, or an organic field effect transistor.

11. A process for the preparation of an electronic device, which process comprises applying a solution and/or dispersion of the polymer according to claim 1 in an organic solvent to a suitable substrate and removing the solvent.

12. A method comprising incorporating the polymer according to claim 1 into organic light emitting diodes, photovoltaic devices, photodiodes, or organic field effect transistors.

13. A compound of the formula

wherein

X 2 and X 2′ are independently of each other halogen, ZnX 12 , —SnR 207 R 208 R 209 , wherein R 207 , R 208 and R 209 are identical or different and are H or C 1 -C 6 alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X 12 is a halogen atom; SiR 210 R 211 R 212 , wherein R 210 , R 211 and R 212 are identical or different and are halogen, or C 1 -C 6 alkyl; —OS(O) 2 CF 3 , —OS(O) 2 -aryl, —OS(O) 2 CH 3 , —B(OH) 2 , —B(OY 1 ) 2 ,

—BF 4 Na or —BF 4 K, wherein Y 1 is independently in each occurrence a C 1 -C 10 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group and Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 10 alkyl group; and A is a unit of the formula

wherein

R 1 is hydrogen, C 1 -C 100 alkyl, or a group of formula —SiR 501 R 502 R 503 ;

R 2 is —CN, —CF 3 , a fluorine atom, or a group of the formula

R 301 , R 302 and R 303 are independently of each other C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E′ and/or interrupted by D′, C 1 -C 100 fluoroalkyl, C 3 -C 12 cycloalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl group, which is substituted by G′; C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 7 -C 25 aralkyl, or C 7 -C 25 aralkyl which is substituted by G′; C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl, which is substituted by G′;

R 601 and R 602 are independently of each other H, or C 1 -C 25 alkyl;

R 501 , R 502 and R 503 are independently of each other C 1 -C 8 alkyl, C 6 -C 24 aryl, or C 7 -C 12 aralkyl;

D′ is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, —NR 65 —, —SiR 70 R 71 —, —POR 72 —, —CR 63 ═CR 64 —, or —C≡C—, and

E′ is —OR 69 , —SR 69 , —NR 65 R 66 , —COR 68 , —COOR 67 , —CONR 65 R 66 , —CN, CF 3 , or halogen,

G′ is E′, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O—,

R 63 and R 64 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—;

R 65 and R 66 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—; or

R′ and R 66 together form a five or six membered ring,

R 67 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,

R 68 is H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,

R 69 is C 6 -C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,

R 70 and R 71 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and

R 72 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl.

14. A process for the preparation of a polymer of formula

comprising reacting a dihalogenide of formula X 10 -A-X 10 with an equimolar amount of a diboronic acid or diboronate corresponding to formula

or reacting a dihalogenide of formula

with an equimolar amount of a diboronic acid or diboronate corresponding to formula X 11 -A-X 11 , wherein X 10 is halogen, and X 11 is independently in each occurrence —B(OH) 2 , —B(OY 1 ) 2 ,

wherein Y 1 is independently in each occurrence a C 1 -C 10 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group and Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 10 alkyl group, in a solvent and in the presence of a catalyst; or

reacting a dihalogenide of formula X 10 -A-X 10 with an equimolar amount of an organo tin compound corresponding to formula

or reacting a dihalogenide of formula

with an equimolar amount of an organo tin compound corresponding to formula X 11′ -A-X 11′ , wherein

X 11′ is independently in each occurrence —SnR 207 R 208 R 209 , wherein R 207 , R 208 and R 209 are identical or different and are H or C 1 -C 6 alkyl, or two of the groups R 207 , R 208 and R 209 form a ring and these groups are optionally branched, A and COM 1 are as defined in claim 4 , X 10 is as defined above and n is in the range of 4 to 1000.