Polymers of benzodithiophene and their use as organic semiconductors

Patent metadata

Field	Value
Publication number	US-10158079-B2
Application number	US-201514674934-A
Country	US
Kind code	B2
Filing date	Mar 31, 2015
Priority date	Apr 19, 2010
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

The invention relates to novel polymers of benzodithiophene, methods and materials for their preparation, their use as semiconductors in organic electronic (OE) devices, and to OE devices comprising these polymers.

First claim

The invention claimed is:

1. A polymer of formula I

wherein
A is on each occurrence identically or differently one of the following groups

B is on each occurrence identically or differently one of the following groups

X 1 and X 2 are each S,
R 1 and R 2 are on each occurrence identically or differently, and independently of each other, —CO—R y , —CO—O—R y , or —O—CO—R y ,
R y is a straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or is aryl or heteroaryl having 2 to 30 C atoms that is unsubstituted or substituted by one or more non-aromatic groups R 5 ,
R 3 and R 4 on each occurrence identically or differently, and independently of each other, denote H, or
primary alkyl, alkoxy or thiolakyl with 1 to 30 C atoms, or secondary alkyl, alkoxy or thioalkyl with 3 to 30 C atoms, or tertiary alkyl, alkoxy or thioalkyl with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F, or
aryl, alkylated aryl or alkoxy aryl with 4 to 40 C atoms,

R 0 and R 00 are independently of each other H or an optionally substituted carbyl or hydrocarbyl group optionally comprising one or more hetero atoms,
Ar is benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]thiadiazole-4,7-diyl, benzo[2,1,3]selenadiazole-4,7-diyl, 5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl, benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyl, benzo[2,1,3]oxadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 2,3-dicyano-1,4-phenylene, 2,5-dicyano,1,4-phenylene, 2,3-difluro-1,4-phenylene, 2,5-difluoro,1,4-phenylene, 2,3,5,6-tetrafluoro,1,4-phenylene, 3,4-difluorothiophene-2,5-diyl, thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl, thieno[3,4-b]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl, or 3,6- pyrrolo[3,4-c]pyrrole-1,4-dione, all of which are unsubstituted, mono- or polysubstituted with halogen, a straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—,—S—,—CO—,—CO—O—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or by an aryl, heteroaryl, aryloxy or heteroaryloxy group having 2 to 40 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 5 , and wherein “alkyl” means a straight-chain or branched alkyl group with 1 to 30 C atoms and “alkoxy” means a straight-chain or branched alkoxy group with 1 to 30 C atoms,
R 5 is on each occurrence identically or differently H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
X 0 is halogen,
m is on each occurrence identically or differently 0 or 1, wherein in at least one repeating unit m is 1,
o is on each occurrence identically or differently 0 or 1, wherein in at least one repeating unit o is 1,
i and k are on each occurrence identically or differently, and independently of each other, 0 or 1, wherein in at least one repeating unit at least one of i and k is 1, and
n is an integer >1.

2. The polymer according to claim 1 , which is of the following formula

wherein R 1-4 , A, B, Ar, i, k, m, n and o on each occurrence identically or differently have the meanings given for the polymer of formula I, and R 6 and R 7 have independently of each other one of the meanings of R 1 , or denote —CH 2 Cl, —CHO, —CH═CH 2 , —SiR′R″R″′, —SnR′R″R″′, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , or P-Sp, wherein P and Sp are as defined for the polymer of formula I, R′, R″ and R′″ have independently of each other one of the meanings of H or an optionally substituted carbyl or hydrocarbyl group optionally comprising one or more hetero atoms, and R′ and R″ may also form a ring together with the hetero atom to which they are attached, and R 0 , R 00 and R 5 are as defined for the polymer of formula I.

3. The polymer according to claim 1 , wherein R 1 and R 2 denote —CO—R y or —CO—O—R y , wherein R y is straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, and wherein in all aforementioned groups one or more H atoms are optionally replaced by F.

4. The polymer according to claim 1 , wherein R 3 and R 4 denote straight-chain or branched alkyl, alkoxy or thioalkyl with 1 to 15 C atoms, wherein one or more H atoms are optionally replaced by F.

5. The polymer according to claim 1 , wherein R 1 and R 2 denote —CO—R y or —CO—O—R y .

6. The polymer according to claim 1 , wherein
Ar is on each occurrence identically or differently benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]thiadiazole-4,7-diyl, benzo[2,1,3]selenadiazole-4,7-diyl, 5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl, benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyl, benzo[2,1,3]oxadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 2,3-dicyano-1,4-phenylene, 2,5-dicyano,1,4-phenylene, 2,3-difluro-1,4-phenylene, 2,5-difluoro,1,4-phenylene, 2,3,5,6-tetrafluoro,1,4-phenylene, 3,4-difluorothiophene-2,5-diyl, thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl, thieno[3,4-]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl, or 3,6-pyrrolo[3,4-c]pyrrole-1,4-dione, all of which are substituted on each occurrence identically or differently, and independently of each other by one or more of the following groups: a straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN.

7. The polymer according to claim 1 , wherein
Ar is on each occurrence identically or differently benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]thiadiazole-4,7-diyl, benzo[2,1,3]selenadiazole-4,7-diyl, 5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl, benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyl, benzo[2,1,3]oxadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 2,3-dicyano-1,4-phenylene, 2,5-dicyano,1,4-phenylene, 2,3-difluro-1,4-phenylene, 2,5-difluoro,1,4-phenylene, 2,3,5,6-tetrafluoro,1,4-phenylene, 3,4-difluorothiophene-2,5-diyl, thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl, thieno[3,4-b]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl, or 3,6-pyrrolo[3,4-c]pyrrole-1,4-dione, all of which are substituted on each occurrence identically or differently, and independently of each other by one or more straight-chain alkoxy groups.

8. The polymer according to claim 1 , wherein
Ar is

Assignees

• Merck Patent Gmbh

Inventors

• Tierney Steven
• Blouin Nicolas
• Mitchell William
• Wang Changsheng
• Carrasco-Orozco Miguel
• Meyer Frank Egon

Classifications

• C07D498/04

  Ortho-condensed systems · CPC title

• C08G2261/411

  Suzuki reactions · CPC title

• C07D513/04

  Ortho-condensed systems · CPC title

• C07D495/04 Primary

  Ortho-condensed systems · CPC title

• C08G2261/414

  Stille reactions · CPC title