Diketopyrrolopyrrole polymers for use in organic semiconductor devices

1. A polymer, comprising:

a unit of formula * A *;

a unit of formula * COM 1 *; and

optionally, a unit of formula* COM 2 *,

wherein A is a repeating unit of formula (I)

wherein

a is 1, 2, or 3,

a′ is 0, 1, 2, or 3,

b is 0, 1, 2, or 3,

b′ is 1, 2, or 3,

c is 0, 1, 2, or 3,

c′ is 0, 1, 2, or 3,

d is 0, 1, 2, or 3,

d′ is 0, 1, 2, or 3,

with the proviso that b′ is not 0, if a′ is 0,

R 1 and R 2 are the same or different and are (a) hydrogen, (b) a C 1 -C 100 alkyl group, (c) —COOR 103 , (c) a C 1 -C 100 alkyl group which is at least one of (i) substituted by at least one halogen atom, hydroxyl group, nitro group, —CN, or C 6 -C 18 aryl group and (ii) interrupted by —O—, —COO—, or —S—, (d) a C 7 -C 100 arylalkyl group, (e) a carbamoyl group, (f) C 5 -C 12 cycloalkyl, which is optionally substituted one to three times with at least one selected from the group consisiting of C 1 -C 8 alkyl and C 1 ,-C 8 alkoxy, (g) a C 6 -C 24 aryl group which is optionally substituted one to three times with at least one selected from the group consisting of C 1 ,-C 8 alkyl, C 1 -C 8 thioalkoxy, and C 1 -C 8 alkoxy, or (h) pentafluorophenyl,

R 103 is C 1 -C 50 alkyl,

Ar 1 and Ar 1′ are independently of each other

wherein one of X 3 and X 4 is N and the other is CR 99 ,

Ar 2 , Ar 2′ , Ar 3 , Ar 3′ , Ar 4 , and Ar 4′ have the meaning of Ar 1 , or are independently of each other

R 99 , R 104 , and R 104′ are independently of each other (i) hydrogen, (j) halogen, (k) a C 1 -C 25 alkyl group which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (1) C 7 -C 25 arylalkyl, or (m) a C 1 -C 25 alkoxy group,

R 105 and R 105′ independently of each other are (n) hydrogen, (o) halogen, (p) C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (q) C 7 -C 25 arylalkyl, or (r) C 1 -C 18 alkoxy,

R 107 is (s) H, (t) 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, (u) C 1 -C 18 alkyl, or (v) C 1 -C 18 alkyl which is interrupted by —O—,

-COM 1 - is a repeating unit of formula

wherein R 9 is C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, C 1 -C 25 perfluoroalkyl, C 1 -C 25 alkoxy, or CN,

-COM 2 - is a second repeating unit -COM 1 - , which is different from the first repeating unit -COM 1 -, a second repeating unit -A-, which is different from the first repeating unit -A-, or a repeating unit of formula

wherein one of X 5 and X 6 is N and the other is CR 114 ,

R 110 is (w) a C 1 -C 25 alkyl group which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (x) C 7 -C 25 arylalkyl, or (y) a C 1 -C 25 alkoxy group

R 111 , R 111′ , R 112 ,and R 112′ are independently of each other (z) hydrogen, (aa) halogen, (ab) a C 1 -C 25 alkyl group which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (ac) C 7 -C 25 arylalkyl, or (ad) a C 1 -C 25 alkoxy group,

R 113 is (ae) C 6 -C 18 aryl, (af) C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, (ag) C 1 -C 18 alkoxy or C 1 -C 18 alkyl, or (ah) C 1 -C 18 alkyl which is interrupted by —O—,

R 114 , R 114′ , R 115 and R 115′ are independently of each other (ai) H or (aj) a C 1 -C 25 alkyl group which is optionally interrupted by at least one oxygen atom,

p is 0, 1, 2, or 3,

r is 0 or 1,

s is 0 or 1,

one of R 106 and R 108 is hydrogen and the other is hydrogen, CN, C 1 -C 8 alkyl, or —COOR 109 ,

R 109 is (ak) C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (al) C 7 -C 25 arylalkyl, or (am) C 6 -C 24 aryl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy;

R 3 and R 3′ are independently of each other (an) hydrogen, (ao) halogen, (ap) C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (aq) C 7 -C 25 arylalkyl, or (ar) C 1 -C 25 alkoxy,

R 4 and R 4′ are independently of each other (as) halogen, (at) C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (au) C 7 -C 25 arylalkyl, or (av) C 1 -C 25 alkoxy;

or two neighboring R 4 and R 4′ groups form a ring with each other,

X 1 and X 2 are independently of each other —O—, —S—, —NR 8 —, —Si(R 11 )(R 11′ )—, —C(R 7 )(R 7′ )—,—C(═O)—,

X 5 is —O— or —NR 8 —,

R 5 and R 5 ′ are independently of each other (aw) hydrogen, (ax) halogen, (ay) C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (az) C 6 -C 24 aryl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, (ba) C 7 -C 25 arylalkyl, (bb) CN, or (bc) C 1 -C 25 alkoxy,

or R 5 and R 5′ together form a ring,

R 55 and R 55′ are independently of each other (bd) H, (be) F, (bf) C 1 -C 18 alkyl, (bg) C 1 -C 18 alkyl which is interrupted by O, (bh) C 1 -C 18 alkoxy, (bi) C 1 -C 18 alkoxy which is interrupted by O, (bj) C 1 -C 18 perfluoroalkyl, (bk) C 6 -C 24 aryl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, or (bl) C 2 -C 20 heteroaryl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy,

R 6 is (bm) H, (bn) C 1 -C 18 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, (bo) C 1 -C 18 perfluoroalkyl, (bp) C 6 -C 24 aryl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, (bq) C 2 -C 20 heteroaryl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, or (br) CN,

R 7 and R 7′ are independently of each other (bs) hydrogen, (bt) C 1 -C 35 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, or (bu) C 7 -C 25 arylalkyl,

R 8 and R 8′ are independently of each other (by) hydrogen, (bw) C 6 -C 18 aryl, (bx) C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 1 8 alkoxy, (by) C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, or (bz) C 7 -C 25 arylalkyl,

R 11 and R 11′ are independently of each other (ca) C 1 -C 35 alkyl group, (cb) C 7 C 25 arylalkyl, or (cc) a phenyl group, which are each optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy,

with the proviso that the following polymer is excluded

(M n =22.7 K; polydispersity=2.1).

2. The polymer of claim 1 , wherein Ar 1 and Ar 1′ are a group of formula

3. The polymer of claim 1 , wherein -COM 1 - is a repeating unit of formula

wherein

R 9 is C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, C 1 -C 25 perfluoroalkyl, C 1 -C 25 alkoxy, or CN.

4. The polymer of claim 1 , wherein A is a group of formula

wherein R 104 and R 104′ are independently of each other hydrogen, a C 1 -C 25 alkyl group which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, C 7 -C 25 arylalkyl, or a C 1 -C 25 alkoxy group.

5. The polymer of claim 1 , wherein R 1 and R 2 independently from each other are

C 1 -C 100 alkyl,

C 5 -C 12 cycloalkyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy,

phenyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy,

1-naphthyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy,

2-naphthyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, or

—CR 101 R 102 —(CH 2 ) u -A 3 , wherein R 101 and R 102 are hydrogen or C 1 -C 4 alkyl,

wherein A 3 is phenyl naphthyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, 1-naphthyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, 2-naphthyl which is optionally substituted one to three times with at least one selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy, and

wherein u is 0, 1, 2, or 3.

6. The polymer of claim 1 , which is a copolymer comprising

(I) wherein A is a group of formula

wherein R 104 and R 104′ are independently of each other hydrogen, a C 1 -C 25 alkyl group which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, C 7 -C 25 arylalkyl, or a C 1 -C 25 alkoxy group,

(II) wherein -COM 1 - is a group of formula

wherein

R 56 and R 56′ independently of each other have the meaning of R 55 , R 9 is C 1 -C 25 alkyl which is optionally interrupted by at least one selected from the group consisting of an oxygen atom and a sulfur atom, C 1 -C 25 perfluoroalkyl, C 1 -C 25 alkoxy, or CN,

(III) wherein -COM 2 - is a second repeating unit -COM 1 - , which is different from the first repeating unit -COM 1 -.

7. The polymer of claim 6 , having a formula

wherein

n is 4 to 1000,

m is 4 to 1000,

R 1 is a C 1 -C 35 alkyl group,

R 3 and R 3′ are H or a C 1 -C 25 alkyl group,

R 5 and R 5′ are a C 1 -C 25 alkyl group or a C 1 -C 25 alkoxy group,

R 55 and R 55′ are H,

R 56 and R 56 ′ are H, a C 1 -C 25 alkyl group, or a C 1 -C 25 alkoxy group,

R 7 , R 7′ , R 11 , and R 11′ are a C 1 -C 35 alkyl group,

R 8 is a C 1 -C 25 alkyl group, and

R 9 is a C 1 -C 25 alkyl group or a C 1 -C 25 alkoxy group.

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

9. A semiconductor device, comprising at least one selected from the group consisting of

the polymer of claim 1 , and

an organic semiconductor material, layer, or component comprising the polymer.

10. The device of claim 9 , which is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.

11. A process for preparing an organic semiconductor device, the process comprising:

applying at least one selected from the group consisting of (i) a solution and (ii) a dispersion of the polymer of claim 1 , in an organic solvent, to a suitable substrate; and

removing the solvent.

12. A process for preparing the polymer of claim 1 , the process comprising:

(A1) reacting a dihalogenide of formula (a11)

X 10 -A-X 10   (a11),

with an equimolar amount of a diboronic acid or diboronate of formula (a12)

X 11 COM 1 X 11   (a12),

or

(A2) reacting a dihalogenide of formula (a21)

X 10 COM 1 X 10   (a21),

with an equimolar amount of a diboronic acid or diboronate of formula (a22)

X 11 -A-X 11   (a22),

in a solvent and in the presence of a catalyst;

or

(A3) reacting a dihalogenide of formula (a31)

X 10 -A-X 10   (a31),

with an equimolar amount of an organo tin compound of formula (a32)

X 11′ COM 1 X 11′   (a32)

or

(A4) reacting a dihalogenide of formula

X 10 COM 1 X 10   (a41),

with an equimolar amount of an organo tin compound formula

X 11′ -A-X 11′   (a42),

to obtain the polymer has a formula (II′)

* A COM 1 *  (II′),

wherein

X 10 is halogen,

X 11 is independently at each occurrence —B(OH) 2 , —B(OY 1 ) 2 ,

Y 1 is independently at each occurrence a C 1 -C 10 alkyl group,

Y 2 is independently at each occurrence a C 2 -C 10 alkylene group, optionally substituted with at least one C 1 -C 10 alkyl group,

Y 13 and Y 14 are independently of each other hydrogen or a C 1 -C 10 alkyl group,

X 11′ is independently at each occurrence —SnR 207 R 208 R 209 ,

R 207 , R 208 , and R 209 are identical or different and are H or optionally branched C 1 -C 6 alkyl,

or two of R 207 , R 208 , and R 209 form a ring.

13. The polymer of claim 1 , wherein at least one selected from the group consisting of R 1 and R 2 is phenyl, 1-naphthyl, or 2-naphthyl.

14. The polymer of claim 1 , wherein at least one selected from the group consisting of R 99 , R 104 , and R 104′ , is F.

15. The polymer of claim 7 , wherein at least one selected from the group of m and n is 4 to 200.

16. The polymer of claim 7 , wherein at least one selected from the group of m and n is 5 to 100.

17. The polymer of claim 7 , wherein R 1 is a C 8 -C 35 alkyl group.