Semiconductor materials prepared from bridged bithiazole copolymers

Patent metadata

Field	Value
Publication number	US-9570688-B2
Application number	US-201514620755-A
Country	US
Kind code	B2
Filing date	Feb 12, 2015
Priority date	Aug 5, 2010
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

The present invention provides semiconducting compounds, oligomers and polymers of formula

wherein
A 1 and A 2 can be the same or different and are S or Se, E is selected from the group consisting of

The compounds, oligomers and polymers of formula of formula (1) are suitable for use in electronic devices such as organic field effect transistors.

First claim

The invention claimed is:

1. An oligomer or polymer of formula

wherein
A 1 and A 2 can be the same or different and are S or Se,
E is selected from the group consisting of

wherein
R 1 is H, halogen, —CN, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-20 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, C 8-10 -cycloalkynyl, C 1-30 -haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, —X 1 —R 6 , —X 2 —Ar 1 , —X 2 —Ar 2 —Ar 1 , —X 2 —Ar 2 —R 7 or —X 2 —Ar 2 —Ar 3 —R 7 ,
wherein
X 1 at each occurrence is independently —O—, —[Z 1 —O] a —, —[O—Z 1 ] a —O—, —S—, —[Z 1 —S—] a —, [S—Z 1 ] a —S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR 8 —, C(O)S—, —O(CO)—, —S(CO)—, —NR 8 C(O)— or —NR 8 —,
wherein
Z 1 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene or C 1-6 -haloalkylene,
a at each occurrence is independently an integer from 1 to 10 and
R 8 at each occurrence is independently H, C 1-20 -alkyl, or —Z 2 —C 6-14 -aryl,
wherein
Z 2 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond,
R 6 at each occurrence is independently C 1-30 -alkyl, C 2-30 -alkenyl or C 1-30 -haloalkyl,
X 2 at each occurrence is independently —Z 3 —O—Z 4 —, —Z 3 —S—Z 4 —, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR 9 , —C(O)S—, —O(CO)—, —S(CO)—, —NR 9 C(O)—, —NR 9 —, —Z 3 —SiR 9 2 —Z 4 —, C 1-30 -alkylene, C 2-30 -alkenylene, C 1-30 -haloalkylene or a covalent bond,
wherein
Z 3 and Z 4 at each occurrence are independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond, and
R 9 at each occurrence is independently H, C 1-20 -alkyl, or —Z 5 —C 6-14 -aryl,
wherein
Z 5 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond,
Ar 1 at each occurrence is independently C 6-14 -aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R a , wherein each R a is independently selected from the group consisting of halogen, CN, C 1-6 -alkyl, C 1-6 -alkoxy and C 1-6 -haloalkyl,
Ar 2 and Ar 3 at each occurrence are independently C 6-14 -arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R b , wherein each R b is independently selected from the group consisting of halogen, CN, C 1-6 -alkyl, C 1-6 -alkoxy and C 1-6 -haloalkyl, and
R 7 at each occurrence is independently C 1-20 -alkyl, C 2-20 -alkenyl, C 1-20 -halaolkyl, C 1-20 -alkoxy, —X 3 —Ar 4 , —X 3 —Ar 5 —Ar 4 , —X 3 —Ar 5 —R 10 , or —X 3 —Ar 5 —Ar 6 —R 10 ,
wherein
X 3 at each occurrence is independently —Z 6 —O—Z 7 —, —Z 6 —S—Z 7 , —S(O)—, —C(O)—, —C(O)O—, —(CO)NR 11 , —C(O)S—, —O(CO)—, —S(CO)—, —NR 11 C(O)—, —NR 11 , —Z 6 —SiR 11 2 —Z 7 —, C 1-30 -alkylene, C 2-30 -alkenylene, C 1-30 -haloalkylene or a covalent bond,
wherein
Z 6 and Z 7 at each occurrence are independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond, and
R 11 at each occurrence is independently H, C 1-20 -alkyl or —Z 8 —C 6-14 -aryl,
wherein
Z 8 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond,
Ar 4 at each occurrence is independently C 6-14 -aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R c , wherein each R c is independently selected from the group consisting of halogen, CN, —C 1-6 -alkyl, C 1-6 -alkoxy and C 1-6 -haloalkyl,
Ar 5 and Ar 6 at each occurrence are independently C 6-14 -arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R d , wherein each R d is independently selected from the group consisting of halogen, CN, C 1-6 -alkyl, C 1-6 -alkoxy and C 1-6 -haloalkyl, and
R 10 at each occurrence is independently C 1-20 -alkyl, C 2-20 -alkenyl, C 1-20 -haloalkyl or C 1-20 -alkoxy,
R 3 , R 4 and R 5 can be the same or different and are H, halogen, —CN, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-20 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, C 8-10 -cycloalkynyl, C 1-30 -haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, —X 4 —R 12 , —X 5 —Ar 7 , —X 5 —Ar 8 —Ar 7 , —X 5 —Ar 8 —R 13 or —X 5 —Ar 8 —Ar 9 —R 13 ,
wherein
X 4 at each occurrence is independently —[Z 9 —O] b —, —[Z 9 —S—] b —, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR 14 — or C(O)S—,
wherein
Z 9 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene or C 1-6 -haloalkylene,
b at each occurrence is independently an integer from 1 to 10 and
R 14 at each occurrence is independently H, C 1-20 -alkyl, or —Z 10 —C 6-14 -aryl,
wherein
Z 10 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond,
R 12 at each occurrence is independently C 1-30 -alkyl, C 2-30 -alkenyl or C 1-30 -haloalkyl,
X 5 at each occurrence is independently —Z 11 —O—Z 12 , —Z 11 —S—Z 12 , —S(O)—, —C(O)—, —C(O)O—, —(CO)NR 15 , —C(O)S—, —Z 11 —SiR 15 2 —Z 12 —, C 1-30 -alkylene, C 2-30 -alkenylene, C 1-30 -haloalkylene or a covalent bond,
wherein
Z 11 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene or C 1-6 -haloalkylene,
Z 12 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond, and
R 15 at each occurrence is independently H, C 1-20 -alkyl, or —Z 13 —C 6-14 -aryl,
wherein
Z 13 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 haloalkylene or a covalent bond,
Ar 7 at each occurrence is independently C 6-14 -aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R e , wherein each R e is independently selected from the group consisting of halogen, CN, C 1-6 -alkyl, C 1-6 -alkoxy and C 1-6 -haloalkyl,
Ar 8 and Ar 9 at each occurrence are independently C 6-14 -arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R f , wherein each R f is independently selected from the group consisting of halogen, CN, C 1-6 -alkyl, C 1-6 -alkoxy and C 1-6 -haloalkyl and
R 13 at each occurrence is independently C 1-20 -alkyl, C 2-20 -alkenyl, C 1-20 -haloalkyl, C 1-20 -alkoxy, —X 6 —Ar 10 , —X 6 —Ar 11 —Ar 10 , —X 6 —Ar 11 —R 16 , or —X 6 —Ar 11 —Ar 12 —R 17 ,
wherein
X 6 at each occurance is independently —Z 14 —O—Z 15 —, —Z 14 —S—Z 15 , —S(O)—, —C(O)—, —C(O)O—, —(CO)NR 18 , —C(O)S—, —O(CO)—, —S(CO)—, —NR 18 C(O)—, —NR 18 —, —Z 14 —SiR 18 2 —Z 15 —, C 1-30 -alkylene, C 2-30 -alkenylene, C 1-30 -haloalkylene or a covalent bond,
wherein
Z 14 and Z 15 at each occurrence are independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond, and
R 18 at each occurrence is independently H, C 1-20 -alkyl or —Z 16 —C 6-14 -aryl,
wherein
Z 16 at each occurrence is independently C 1-6 -alkylene, C 2-6 -alkenylene, C 1-6 -haloalkylene or a covalent bond,
Ar 10 at each occurrence is independently C 6-14 -aryl or monovalent 5 to 14 membered aromatic heterocyclic res

Assignees

• Basf Se
• Polyera Corp

Inventors

• Mishra Ashok Kumar
• Vaidyanathan Subramanian
• Noguchi Hiroyoshi
• Doetz Florian
• Zhu Bo
• Basuki Johan Sebastian

Classifications

• H10K10/46

  Field-effect transistors, e.g. organic thin-film transistors [OTFT] (H10K10/43 takes precedence) · CPC title

• H10K85/655

  comprising only sulfur as heteroatom · CPC title

• H10K85/657 Primary

  Polycyclic condensed heteroaromatic hydrocarbons · CPC title

• C07D513/14

  Ortho-condensed systems · CPC title

• C08G2261/414

  Stille reactions · CPC title