US20130144065A1

US20130144065A1 - Semiconductor materials prepared from bridged bithiazole copolymers

Info

Publication number: US20130144065A1
Application number: US13/810,819
Authority: US
Inventors: Ashok Kumar Mishra; Subramanian Vaidyanathan; Hiroyoshi Noguchi; Florian Doetz; Bo Zhu; Johan Sebastian Basuki
Original assignee: BASF SE; Polyera Corp
Current assignee: BASF SE; Flexterra Inc
Priority date: 2010-08-05
Filing date: 2011-07-29
Publication date: 2013-06-06
Also published as: US9570688B2; JP5693722B2; EP2601236A2; EP2601236B1; KR20130052623A; JP2013538257A; CN103052643B; WO2012016925A3; KR101522112B1; CN103052643A; WO2012016925A2; US20150162546A1

Abstract

The present invention provides semiconducting compounds, oligomers and polymers of formula wherein A¹and A²can 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.

Description

Organic semiconducting materials can be used in electronic devices such as organic photovoltaic (OPV) cells, organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).
It is desirable that the organic semiconducting materials are compatible with liquid processing techniques such as spin coating, solution casting or printing. Liquid processing techniques are convenient from the point of processability, and can also be applied to plastic substrates. Thus, organic semiconducting materials which are compatible with liquid processing techniques allow the production of low cost, light weight and, optionally also flexible, electronic devices, which is a clear advantage of these organic semiconducting materials compared to inorganic semiconducting materials.
Furthermore, it is desirable that the organic semiconducting materials are stable, in particular towards oxidation.
When used in organic field-effect transistors (OFETs), the organic semiconducting materials should show a high charge carrier mobility and a high on/off ratio.
The use of organic semiconducting materials in electronic devices, in particular in organic field effect transistors (OFETs) is known in the art.
Fuchigami, H.; Tsumura, A.; Koezuka, H. Appl. Phys. Lett. 1993, 63, 1372-1374 describes the use of poly(2,5-thienylenevinylene) in field-effect transistors.
Bao, Z.; Dobadalapur, A.; Lovinger, A. J. Appl. Phys. Lett. 1996, 69, 4108-4110 describes the use of regioregular poly(3-hexylthiophene) in field-effect transistors.
Zhang, M.; Tsao, H. N.; Pisula, W.; Yang, C.; Mishra, A. K.; Mullen, K. J. Am. Chem. Soc. 2007, 129, 3472-3473 describes polymers of formula
for use in organic field effect transistors (OFETs).
Xiao, S; Zhou H.; You, W. Macromolecules 2008, 41, 5688-5696 describes the following polymers
as donor materials for use in photovoltaic devices.
Scharber, M. C.; Koppe, M.; Gao, J.; Cordella, F.; Loi, M. A.; Denk, P.; Morana, M.; Egelhaaf, H.-J.; Forberich, K.; Dennler, G.; Gaudiana, R.; Waller, D.; Zhu, Z.; Shi, X.; Brabec, C. J. Adv. Mater. 2009, 21, 1-4 describes the following polymers
as donor materials for use in solar cells.
Rieger, R.; Beckmann, D.; Pisula, W.; Steffen, W.; Kastler, M.; Müllen K. Adv. Mater. 2010, 22, 83-86 describes the following polymers
for use in organic field-effect transistor (OFET).
Kim, D. H.; Lee, B.-L-; Moon, H.; Kang, H. M.; Jeong, E. J.; Park, J.; Han, K.-M.; Lee, S.; Yoo, B. W.; Koo, B. W.; Kim, J. Y.; Lee, W. H.; Cho, K.; Becerril, H. A.; Z. Bao Z. J. Am. Chem. Soc. 2009, 131, 6124-6132 describes the polymer
for use in organic field effect transistors (OFETs).
Osaka, I.; Sauvé, G.; Zhang, R.; Kowalewski, T.; McCullough R. D. Adv. Mater. 2007, 19, 4160-4165 describes the polymers
for use in organic field effect transistors (OFETs).
EP 2 085 401 A1 describes benzobisthiazole polymers comprising a unit having the following formula
wherein each of R¹, R², R³and R⁴represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted thioalkoxy group, wherein at least one of R¹, R², R³and R⁴is not a hydrogen atom, and n is a positive integer, wherein when n is 2 or more, each of R³is the same as or different from the others and each of R⁴is the same or different from the others,
for use in transistors.
US 2008/0121281 A1 describes photovoltaic cells with thiazole-containing polymers such as bithiazole-containing polymers, cyclopentadithiazole-containing polymers or thiazolothiazole-containing polymers. Cyclopentadithiazole-containing polymers can be polymers which include a first comonomer repeat unit comprising a cyclopentadithiazole moiety, and a second comonomer repeat unit different from the first comonomer repeat unit. In some embodiments, the first comonomer repeat unit includes a cyclopentadithiazole moiety of formula
in which each of R¹and R², independently, is H, C_1-20-alkyl, C_1-20-alkoxy, C_3-20-cycloalkyl, C_1-20-heterocycloalkyl, aryl, heteroaryl, halo, CN, OR, C(O)R, C(O)OR, or SO₂R; R being H, C_1-20-alkyl, C_1-20-alkoxy, C_3-20-cycloalkyl, C_1-20-heterocycloalkyl, aryl, or heteroaryl.
WO 2009/069687 describes a polymer represented by the general formula
wherein Z²¹and Z²²independently represent, for example, —S—.
It is the object of the present invention to provide organic semiconducting materials suitable for use in electronic devices, in particular in organic field effect transistors (OFETs), where the organic semiconducting materials show a high oxidative stability, particularly in ambient conditions, and are compatible with liquid processing techniques. The organic field effect transistors comprising the organic semiconducting materials should show an acceptable charge carrier mobility and current on/off ratio.
This object is solved by the compound, oligomer or polymer of claim 1 and the electronic device of claim 19.
The compound, oligomer or polymer of the present invention are of formula
wherein
A¹and A²can be the same or different and are S or Se,
E is selected from the group consisting of

- wherein
- R¹and R²can 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, —X¹—R⁶, —X²—Ar¹, —X²—Ar²—Ar¹, —X²—Ar²—R⁷or —X²—Ar²—Ar³—R⁷,
  - wherein
  - X¹at each occurrence is independently —O—, —[Z¹—O]_a—, —[O—Z¹]_a—O—, —S—, —[Z¹—S—]_a—, —[S—Z¹]_a—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR⁸—, C(O)S—, —O(CO)—, —S(CO)—, —NR⁸C(O)— or —NR⁸—,
    - wherein
    - Z¹at 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
    - R⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²—C_6-14-aryl,
      - wherein
      - Z²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R⁶at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X²at each occurrence is independently —Z³—O—Z⁴—, —Z³—S—Z⁴—, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR⁹, —C(O)S—, —C(O)—, —S(O)—, —NR⁹C(O)—, —NR⁹—, —Z³—SiR⁹ ₂—Z⁴—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z³and Z⁴at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R⁹at each occurrence is independently H, C_1-20-alkyl, or —Z⁵—C_6-14-aryl,
      - wherein
      - Z⁵at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar²and Ar³at 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^bis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X³—Ar⁴, —X³—Ar⁵—Ar⁴, —X³—Ar⁵—R¹⁰, or —X³—Ar⁵—Ar⁶—R¹⁰,
    - wherein
    - X³at each occurrence is independently —Z⁶—O—Z⁷—, —Z⁶—S—Z⁷, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR¹¹, —C(O)S—, —C(O)—, —S(O)—, —NR¹¹C(O)—, —NR¹¹—, —Z⁶—SiR¹¹ ₂—Z⁷—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z⁶and Z⁷at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R¹¹at each occurrence is independently H, C_1-20-alkyl or —Z⁸—C_6-14-aryl,
      - wherein
      - Z⁸at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar⁴at 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^cis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar⁵and Ar⁶at 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^dis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
    - R¹⁰at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
- R³, R⁴and R⁵can 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, —X⁴—R¹², —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,
  - wherein
  - X⁴at each occurrence is independently —[Z⁹—O]_b—, —[Z⁹—S—]_b—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁴— or C(O)S—,
    - wherein
    - Z⁹at 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
    - R¹⁴at each occurrence is independently H, C_1-20-alkyl, or —Z¹⁰—C_6-14-aryl,
      - wherein
      - Z¹⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R¹²at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁵at each occurrence is independently —Z¹¹—O—Z¹², —Z¹¹—S—Z¹²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁵, —C(O)S—, —Z¹¹—SiR¹⁵ ₂—Z¹²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z¹¹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - Z¹²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R¹⁵at each occurrence is independently H, C_1-20-alkyl, or —Z¹³—C_6-14-aryl,
      - wherein
      - Z¹³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar⁷at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl and
  - R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁶—Ar¹⁰, —X⁶—Ar¹¹—Ar¹⁰, —X⁶—Ar¹¹—R¹⁶, or —X⁶—Ar¹¹—Ar¹²—R¹⁷,
    - wherein
    - X⁶at each occurrence is independently —Z¹—O—Z¹⁵—, —Z¹⁴—S—Z¹⁵, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁸, —C(O)S—, —C(O)—, —S(O)—, —NR¹⁸C(O)—, —NR¹⁸—, —Z¹⁴—SiR¹⁸ ₂—Z¹⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z¹⁴and Z¹⁵at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R¹⁸at each occurrence is independently H, C_1-20-alkyl or —Z¹⁶—C_6-14-aryl,
      - wherein
      - Z¹⁶at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar¹⁰at 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^g, wherein each R^gis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar¹¹and Ar¹²at 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^h, wherein each R^his independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl and
    - R¹⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
- R¹⁹is O or C(CN)₂, and
- R²⁰and R²¹are the same or different and are R²²or CN,
  - wherein R²²has the same meaning as R¹,
    G¹and G²are the same or different and are phenylene or a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, which phenylene and monocyclic bivalent to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R, wherein each R is independently selected from the group consisting of halogen, —CN, —NO₂, —OH, C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_5-10-cycloalkenyl, —Z¹⁷—C_8-10-cycloalkynyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
    wherein C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_5-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R, wherein each R is independently selected from the group consisting of halogen, —CN, —NO₂, *═O, —OH, —NH₂, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_mH, —S(O)_m—C_1-20-alkyl, —S(O)₂OH, —S(O)_m—OC_1-20-alkyl, —S(O)_m—OC_1-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)OH, —C(O)—OC_1-20-alkyl, —C(O)—CO_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_mNH₂, —S(O)_mNH(C_1-20-alkyl), —S(O)_mN(C_1-20-alkyl)₂, —S(O)_mNH(C_6-14-aryl), —S(O)_mN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_mN(C_6-14-aryl)₂, SiH₃, SiH(C_1-20-alkyl)₂, SiH₂(C_1-20-alkyl) and Si(C_1-20-alkyl)₃, and
    wherein C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_2-20-alkenyl, C_2-20-alkynyl, C_1-20-alkoxy, C_1-20-haloalkyl,
- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- m at each occurrence is independently 0, 1 or 2,
  L is C_6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein C_6-24-arylene and bivalent 5 to 18 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^l, wherein each R^lis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, OH, *═C(C_1-30-alkyl)₂, C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_5-10-cycloalkenyl, —Z¹⁸—C_8-10-cycloalkynyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent to 14 membered aromatic heterocyclic residue,
  wherein C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_5-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, —OH, —NH₂, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_oH, —S(O)_o—C_1-20-alkyl, —S(O)₂OH, —S(O)_o—C_1-20-alkyl, —S(O)_o—OC_6-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)OH, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_oNH₂, —S(O)ONH(C_1-20-alkyl), —S(O)_oN(C_1-20-alkyl)₂, —S(O)ONH(C_6-14-aryl), —S(O)_oN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_oN(C_6-14-aryl)₂, SiH₃, SiH(C_1-20-alkyl)₂, SiH₂(C_1-20-alkyl) and Si(C_1-20-alkyl)₃, and
  wherein C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl, C_2-20-alkenyl, C_2-20-alkynyl, C_1-20-alkoxy, —S—C_1-20-alkyl, C_1-20-haloalkyl,
  wherein
  Z¹⁸at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
  o at each occurrence is independently 0, 1 or 2,
  or

L is

- wherein
- R²³and R²⁴can be the same or different and are H, halogen, —CN, C_1-30alkyl, 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, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,
  - wherein
  - X⁷at each occurrence is independently —O—, —[Z¹⁹—O]_c—, [O—Z¹⁹]_c—O—, —S—, —[Z¹⁹—S—]_c—, —[S—Z¹⁹]_c—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR²⁷—, C(O)S—, —C(O)—, —S(O)—, —NR²⁷C(O)— or —NR²⁷—,
    - wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
    - R²⁷at each occurrence is independently H, C_1-20-alkyl, or —Z²⁰—C_6-14-aryl,
      - wherein
      - Z²⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R²⁵at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently —Z²¹—O—Z²², —Z²¹—S—Z²²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR²⁸, —C(O)S—, —C(O)—, —S(O)—, —NR²⁸C(O)—, —NR²⁸—, —Z²¹—SiR²⁸ ₂—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R²⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²³—C_6-14-aryl,
      - wherein
      - Z²³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹³at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar¹⁴and Ar¹⁵at 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^p, wherein each R^pis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁹—Ar¹⁶, —X⁹—Ar¹⁷—Ar¹⁶, —X⁹—Ar¹⁷—R²⁹, or —X⁹—Ar¹⁷—Ar¹⁸—R²⁹,
    - wherein
    - X⁹at each occurrence is independently —Z²⁴—O—Z²⁵—, —Z²⁴—S—Z²⁵, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR³⁰, —C(O)S—, —C(O)—, —S(O)—, —NR³⁰C(O)—, —NR³⁰—, —Z²⁴—SiR³⁰ ₂—Z²⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z²⁴and Z²⁵at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R³⁰at each occurrence is independently H, C_1-20-alkyl or —Z²⁶—C_6-14-aryl,
      - wherein
      - Z²⁶at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar¹⁶at 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^q, wherein each R^qis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar¹⁷and Ar¹⁸at 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^r, wherein each R^ris independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
    - R²⁹at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
      q and s are the same or different and are 0, 1, 2, 3, 4 or 5,
      r is 0, 1 or 2,
      and
      n is an integer from 1 to 10'000.

Preferred are oligomers or polymers of formula
wherein
A¹and A²can be the same or different and are S or Se,
E is selected from the group consisting of

- wherein
- R¹and R²can 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, —X¹—R⁶, —X²—Ar¹, —X²—Ar²—Ar¹, —X²—Ar²—R⁷or —X²—Ar²—Ar³—R⁷,
  - wherein
  - X¹at each occurrence is independently —O—, —[Z¹—O]_a—, —[O—Z¹]_a—O—, —S—, —[Z¹—S]_a—, —[S—Z¹]_a—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR⁸—, C(O)S—, —O(CO)—, —S(CO)—, —NR⁸C(O)— or —NR⁸—,
    - wherein
    - Z′ 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
    - R⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²—C_6-14-aryl,
      - wherein
      - Z²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R⁶at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X²at each occurrence is independently —Z³—O—Z⁴—, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR⁹, —C(O)S—, —O(CO)—, —S(CO)—, —NR⁹C(O)—, —NR⁹—, —Z³—SiR⁹ ₂—Z⁴—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z³and Z⁴at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R⁹at each occurrence is independently H, C_1-20-alkyl, or —Z⁵—C_6-14-aryl,
      - wherein
      - Z⁵at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar²and Ar³at 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^bis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X³—Ar⁴, —X³—Ar⁵—Ar⁴, —X³—Ar⁵—R¹⁰, or —X³—Ar⁵—Ar⁶—R¹⁰,
    - wherein
    - X³at each occurrence is independently —Z⁶—O—Z⁷—, —Z⁶—S—Z⁷, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹¹, —C(O)S—, —C(O)—, —S(O)—, —NR¹¹C(O)—, —NR¹¹—, —Z⁶—SiR¹¹ ₂—Z⁷—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z⁶and Z⁷at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R¹¹at each occurrence is independently H, C_1-20-alkyl or —Z⁸—C_6-14-aryl,
      - wherein
      - Z⁸at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar⁴at 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^cis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar⁵and Ar⁶at 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^dis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
    - R¹⁰at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
- R³, R⁴and R⁵can 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_6-10-cycloalkenyl, C_8-10-cycloalkynyl, C_1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, —X⁴—R¹², —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,
  - wherein
  - X⁴at each occurrence is independently —[Z⁹—O]_b—, —[Z⁹—S—]_b—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁴— or C(O)S—,
    - wherein
    - Z⁹at 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
    - R¹⁴at each occurrence is independently H, C_1-20-alkyl, or —Z¹⁰—C_6-14-aryl,
      - wherein
      - Z¹⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R¹²at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁵at each occurrence is independently —Z¹¹—O—Z¹², —Z¹¹—S—Z¹²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁵, —C(O)S—, —Z¹¹—SiR¹⁵ ₂—Z¹²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z¹¹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - Z¹²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R¹⁵at each occurrence is independently H, C_1-20-alkyl, or —Z¹³—C_6-14-aryl,
      - wherein
      - Z¹³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar⁷at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl and
  - R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁶—Ar¹⁰, —X⁶—Ar¹¹—Ar¹⁰, —X⁶—Ar¹¹—R¹⁶, or —X⁶—Ar¹¹—Ar¹²—R¹⁷,
    - wherein
    - X⁶at each occurrence is independently —Z¹⁴—O—Z¹⁵—, —Z¹⁴—S—Z¹⁵, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁸, —C(O)S—, —C(O)—, —S(O)—, —NR¹⁸C(O)—, —NR¹⁸—,
    - —Z¹⁴—SiR¹⁸ ₂—Z¹⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z¹⁴and Z¹⁵at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R¹⁸at each occurrence is independently H, C_1-20-alkyl or —Z¹⁶—C_6-14-aryl,
      - wherein
      - Z¹⁶at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar¹⁰at 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^g, wherein each R^gis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar¹¹and Ar¹²at 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^h, wherein each R^his independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl and
    - R¹⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
- R¹⁹is O or C(CN)₂, and
- R²⁰and R²¹are the same or different and are R²²or CN,
  - wherein R²²has the same meaning as R¹,
    G¹and G²are the same or different and are phenylene or a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, which phenylene and monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R, wherein each R is independently selected from the group consisting of halogen, —CN, —NO₂, —OH, C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_6-10-cycloalkenyl, —Z¹⁷—C_8-10-cycloalkynyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
    wherein C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_6-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R, wherein each R is independently selected from the group consisting of halogen, —CN, —NO₂, *═O, —OH, —NH₂, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_mH, —S(O)_m—C_1-20-alkyl, —S(O)₂OH, —S(O)_m—OC_1-20-alkyl, —S(O)_m—OC_6-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)OH, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_mNH₂, —S(O)_mNH(C_1-20-alkyl), —S(O)_mN(C_1-20-alkyl)₂, —S(O)_mNH(C_6-14-aryl), —S(O)_mN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_mN(C_6-14-aryl)₂, SiH₃, SiH(C_1-20-alkyl)₂, SiH₂(C_1-20-alkyl) and Si(C_1-20-alkyl)₃, and
    wherein C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_2-20-alkenyl, C_2-20-alkynyl, C_1-20-alkoxy, —S—C_1-20-alkyl, C_1-20-haloalkyl,
- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- m at each occurrence is independently 0, 1 or 2,
  L is C_6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein C_6-24-arylene and bivalent 5 to 18 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^l, wherein each R^lis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, OH, *═C(C_1-30-alkyl)₂, C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_5-10-cycloalkenyl, —Z¹⁸—C_8-10-cycloalkynyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,
  wherein C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_5-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, —OH, —NH₂, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_oH, —S(O)_o—C_1-20-alkyl, —S(O)₂OH, —S(O)_o—OC_1-20-alkyl, —S(O)_o—OC_6-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)OH, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_oNH₂, —S(O)ONH(C_1-20-alkyl), —S(O)_oN(C_1-20-alkyl)₂, —S(O)ONH(C_6-14-aryl), —S(O)_oN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_oN(C_6-14-aryl)₂, SiH₃, SiH(C_1-20-alkyl)₂, SiH₂(C_1-20-alkyl) and Si(C_1-20-alkyl)₃, and
  wherein C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl, C_2-20-alkenyl, C_2-20-alkynyl, C_1-20-alkoxy, C_1-20-haloalkyl,
  wherein
  Z¹⁸at each occurrence is independently C_1-6-alkylene, C_1-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
  o at each occurrence is independently 0, 1 or 2,
  or

L is

- wherein
- R²³and R²⁴can 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, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,
  - wherein
  - X⁷at each occurrence is independently —O—, —[Z¹⁹—O]_c—, [O—Z¹⁹]_c—O—, —S—, —[Z¹⁹—S—]_c—, —[S—Z¹⁹]_c—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR²⁷—, C(O)S—, —O(CO)—, —S(CO)—, —NR²⁷C(O)— or —NR²⁷—,
    - wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
    - R²⁷at each occurrence is independently H, C_1-20-alkyl, or —Z²⁰—C_6-14-aryl,
      - wherein
      - Z²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R²⁵at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR²⁸, —C(O)S—, —C(O)—, —S(O)—, —NR²⁸C(O)—, —NR²⁸—, —Z²¹—SiR²⁸ ₂—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R²⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²³—C_6-14-aryl,
      - wherein
      - Z²³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹³at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar¹⁴and Ar¹⁵at 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^p, wherein each R^pis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁹—Ar¹⁶, —X⁹—Ar¹⁷—Ar¹⁶, —X⁹—Ar¹⁷—R²⁹, or —X⁹—Ar¹⁷—Ar¹⁸—R²⁹,
    - wherein
    - X⁹at each occurrence is independently —Z²⁴—O—Z²⁵—, —Z²⁴—S—Z²⁵, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR³⁰, —C(O)S—, —C(O)—, —S(O)—, —NR³⁰C(O)—, —NR³⁰—, —Z²⁴—SiR³⁰ ₂—Z²⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z²⁴and Z²⁵at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R³⁰at each occurrence is independently H, C_1-20-alkyl or —Z²⁶—C_6-14-aryl,
      - wherein
      - Z²⁶at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar¹⁶at 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^q, wherein each R^qis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar¹⁷and Ar¹⁸at 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^r, wherein each R^ris independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
    - R²⁹at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
      q and s are the same or different and are 0, 1, 2, 3, 4 or 5,
      r is 0, 1 or 2,
      and
      n is an integer from 2 to 10'000.

Examples of halogen are —F, —Cl, —Br and —I.
Examples of C_1-6-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl and n-hexyl. Examples of C_1-20-alkyl are C_1-6-alkyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀). Examples of C_1-30-alkyl are C_1-20-alkyl, n-docosyl (C₂₂), n-tetracosyl (C₂₄), n-hexacosyl (C₂₆), n-octacosyl (C₂₈) and n-triacontyl (C₃₀).
Examples of C_1-6-haloalkyl are CF₃, CHF₂, CH₂F, C₂F₅, CH₂(CH₂)₄CF₃, CF₃, CCl₃, CHCl₂, CH₂Cl, C₂Cl₅and CH₂(CH₂)—CCl₃. Examples of C_1-20-haloalkyl and of C_1-30-haloalkyl are C_1-6-haloalkyl and CH₂(CH₂)₈CF₃, CH₂(CH₂)₁₄CF₃.
Examples of C_1-6-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, isopentoxy and n-hexoxy. Examples of C_1-20-alkoxy are C_1-6-alkoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy, n-undecoxy, n-dodoxy, n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxy, n-nonadecoxy and n-eicosoxy (C₂₀).
Examples of C_2-20-alkenyl are ethenyl, propenyl, cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis-2-pentenyl, trans-2-pentenyl, cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl, docenyl, undocenyl and oleyl (C₁₈). Examples of C_2-20-alkenyl are also butadienyl, pentadienyl, hexadienyl, linoleyl (C₁₈), linolenyl (C₁₈) and arachidonyl (C₂₀). Examples of C_2-30-alkenyl are C_2-20-alkenyl and erucyl (C₂₂).
Examples of C_2-20-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl and icosynyl (C₂₀). Examples of C_2-30-alkynyl are C_2-20-alkynyl.
Examples of C_3-10-cycloalkyl are preferably monocyclic C_3-10-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic C_3-10-cycloalkyls such as decalinyl, norbornyl and adamantyl.
Examples of C_5-10-cycloalkenyl are preferably monocyclic C_5-10-cycloalkenyls such as cyclopentenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic C_5-10-cycloalkenyls.
An example of C_8-10-cycloalkynyl is cyclooctynyl.
The monovalent 3 to 12 membered aliphatic heterocyclic residues can be monocyclic monovalent 3 to 8 membered aliphatic heterocyclic residues or polycyclic, for example bicyclic, monovalent 7 to 12 membered aliphatic heterocyclic residues.
Examples of monocyclic monovalent 3 to 8 membered aliphatic heterocyclic residues are monocyclic monovalent 5 membered aliphatic heterocyclic residues containing one heteroatom such as pyrrolidinyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and 2,3-dihydrothiophenyl, monocyclic monovalent 5 membered aliphatic heterocyclic residues containing two heteroatoms such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thiazolinyl, isothiazolidinyl and isothiazolinyl, monocyclic monovalent 5 membered aliphatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazolyl, 1,2,4-triazolyl and 1,4,2-dithiazolyl, monocyclic monovalent 6 membered aliphatic heterocyclic residues containing one heteroatom such as piperidyl, piperidino, tetrahydropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic monovalent 6 membered aliphatic heterocyclic residues containing two heteroatoms such as piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic monovalent 7 membered aliphatic heterocyclic residues containing one hereoatom such as azepanyl, azepinyl, oxepanyl, thiepanyl, thiapanyl, thiepinyl, and monocyclic monovalent 7 membered aliphatic heterocyclic residues containing two hereoatom such as 1,2-diazepinyl and 1,3-thiazepinyl.
The monovalent 3 to 12 membered aliphatic heterocyclic residues can contain one or more heteroatoms, which can independently be selected from the group consisting of nitrogen, oxygen, sulfur, phosphor, silicon and arsenic, preferably from the group consisting of nitrogen, oxygen and sulfur.
Examples of monocyclic monovalent 3 to 12 membered aliphatic heterocyclic residue substituted with *═O are 2-oxazolidonyl, 4-piperidonyl, 4-piperidono, pyrimidine-2,4(1H,3H)-dionyl and 2-pyridonyl.
An example of a bicyclic monovalent 7 to 12 membered aliphatic heterocyclic residue is decahydronaphthyl.
C_6-14-aryl can be monocyclic or polycyclic. Examples of C_6-14-aryl are monocyclic C₆-aryl such as phenyl, bicyclic C_9-10-aryl such as 1-naphthyl, 2-naphthyl, indenyl, indanyl and tetrahydronaphthyl, and tricyclic C_12-14-aryl such as anthryl, phenanthryl, fluorenyl and s-indacenyl.
C_6-14-haloaryl can be monocyclic or polycyclic. Examples of C_6-14-haloaryl are 6-chlorophenyl and 2-chlorophenyl.
The monovalent 5 to 14 membered aromatic heterocyclic residues can be monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues, or polycyclic monovalent 7 to 12 membered aromatic heterocyclic residues, for example bicyclic or tricyclic monovalent 9 to 14 membered aromatic heterocyclic residues.
Examples of monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues are monocyclic monovalent 5 membered aromatic heterocyclic residues containing one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazolyl, 1,2,4-triazolyl and oxadiazolyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing four heteroatoms such as tetrazolyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing one heteroatom such as pyridyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing two heteroatoms such as pyrazinyl, pyrimidinyl and pyridazinyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazinyl, 1,2,4-triazinyl and 1,3,5-triazinyl, monocyclic monovalent 7 membered aromatic heterocyclic residues containing one heteroatom such as azepinyl, and monocyclic monovalent 7 membered aromatic heterocyclic residues containing two heteroatoms such as 1,2-diazepinyl,
Examples of bicyclic monovalent 7 to 12 membered aromatic heterocyclic residues are bicyclic 9 membered aromatic heterocyclic residues containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, benzothiophenyl and isobenzothiophenyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxazolopyridyl, thiazolopyridyl, isothiazolopyridyl and imidazopyridyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing four heteroatoms such as purinyl, bicyclic monovalent 10 membered aromatic heterocyclic residues containing one heteroatom such as quinolyl, isoquinolyl, chromenyl and chromanyl, bicyclic monovalent 10 membered aromatic heterocyclic residues containing two heteroatoms such as quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, 1,5-naphthyridinyl and 1,8-naphthyridinyl, bicyclic monovalent 10 membered aromatic heterocyclic residues containing three heteroatoms such as pyridopyrazinyl, pyridopyrimidinyl and pyridopyridazinyl, and bicyclic monovalent 10 membered aromatic heterocyclic residues containing four heteroatoms such as pteridinyl.
Examples of tricyclic monovalent 9 to 14 membered aromatic heterocyclic residues are dibenzofuryl, acridinyl, phenoxazinyl, 7H-cyclopenta[1,2-b:3,4-b]dithiophenyl and 4H-cyclopenta[2,1-b:3,4-b]dithiophenyl.
The monovalent 5 to 14 membered aromatic heterocyclic residue can contain one or more heteroatoms which can independently be selected from the group consisting of nitrogen, oxygen, sulfur, phosphor, silicon and arsenic, preferably from the group consisting of nitrogen, oxygen and sulfur.
Examples of C_1-6-alkylene are methylene, ethylene, butylene, pentylene, hexylene and 2-methylpentylene. Examples of C_1-30-alkylene are C_1-6-alkylene, CH₂(CH₂)₁₀CH₂and CH₂(CH₂)₂₀)CH₂.
Examples of C_2-6-alkenylene are ethenylene, cis-2-butenylene, trans-butenylene, cis-2-pentenylene, trans-2-pentenylene, trans-2-hexenylene, trans-3-hexenylene and 2-methyl-trans-3-pentenylene. Examples of C_2-30-alkenylene are C_2-6-alkenylene, CH₂(CH₂)₄—CH═CH—(CH₂)₄CH₂and CH₂(CH₂)₉—CH═CH—(CH₂)₉CH₂.
Examples of C_1-6-haloalkylene are CF₂, CCl₂, CF₂CF₂, CCl₂CCl₂, CHFCH₂, CHFCH₂CH₂CHF and CHF(CH₂)₄CHF. Examples of C_1-30-haloalkylene are C_1-6-haloalkylene, CHF(CH₂)₁₀CHF and CHF(CH₂)₂₀CHF.
Examples of C_6-14-arylene are monocyclic C₆-arylene such as phenylene, bicyclic C_9-10-arylene such as 1-naphthylene, 2-naphthyl, indenylene, indanylene and tetrahydronaphthylene, and tricyclic C_12-14-arylene such as anthrylene, phenanthrylene, fluorenylene and s-indacenylene. Examples of C_6-24-arylene are C_6-14-arylene and pyrenylene, tetracenylene, perylenylene, indenofluorenylene, pentacenylene, coronenylene and tetraphenylenylene.
The bivalent 5 to 14 membered aromatic heterocyclic residues can be monocyclic bivalent 5 to 8 membered aromatic heterocyclic residues, or polycyclic bivalent 7 to 12 membered aromatic heterocyclic residues, for example bicyclic or tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues.
Examples of monocyclic bivalent 5 to 8 membered aromatic heterocyclic residues are monocyclic bivalent 5 membered aromatic heterocyclic residues containing one heteroatom such as pyrrolylene, furylene and thiophenylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing two heteroatoms such as imidazolylene, pyrazolylene, oxazolylene, isoxazolylene, thiazolylene, isothiazolylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazolylene, 1,2,4-triazolylene and oxadiazolylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing four heteroatoms such as tetrazolylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing one heteroatom such as pyridylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing two heteroatoms such as pyrazinylene, pyrimidinylene and pyridazinylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing three heteroatoms such as 1,2,3-triazinylene, 1,2,4-triazinylene and 1,3,5-triazinylene, monocyclic bivalent 7 membered aromatic heterocyclic residues containing one heteroatom such as azepinylene, and monocyclic bivalent 7 membered aromatic heterocyclic residues containing two heteroatoms such as 1,2-diazepinylene.
Examples of bicyclic bivalent 7 to 12 membered aromatic heterocyclic residues are bicyclic bivalent 9 membered aromatic heterocyclic residues containing one heteroatom such as indolylene, isoindolylene, indolizinylene, indolinylene, benzofurylene, isobenzofurylene, benzothiophenylene and isobenzothiophenylene, bicyclic bivalent 9 membered aromatic heterocyclic residues containing two heteroatoms such as indazolylene, benzimidazolylene, benzimidazolinylene, benzoxazolylene, benzisooxazolylene, benzthiazolylene, benzisothiazolylene, furopyridylene and thienopyridylene, bicyclic bivalent 9 membered aromatic heterocyclic residues containing three heteroatoms such as benzotriazolylene, benzoxadiazolylene, oxazolopyridylene, isooxazolopyridylene, thiazolopyridylene, isothiazolopyridylene and imidazopyridylene, bicyclic bivalent 9 membered aromatic heterocyclic residues containing four heteroatoms such as purinylene, bicyclic bivalent 10 membered aromatic heterocyclic residues containing one heteroatom such as quinolylene, isoquinolylene, chromenylene and chromanylene, bicyclic bivalent 10 membered aromatic heterocyclic residues containing two heteroatoms such as quinoxalinylene, quinazolinylene, cinnolinylene, phthalazinylene, 1,5-naphthyridinylene and 1,8-naphthyridinylene, bicyclic bivalent 10 membered aromatic heterocyclic residues containing three heteroatoms such as pyridopyrazinylene, pyridopyrimidinylene and pyridopyridazinylene, and bicyclic bivalent 10 membered aromatic heterocyclic residues containing four heteroatoms such as pteridinylene.
Examples of tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues containing one heteroatom are dibenzofurylene and acridinylene. Examples of a tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues containing two heteroatoms are phenoxazinylene, 7H-cyclopenta[1,2-b:3,4-b′]dithiophenylene and 4H-cyclopenta[2,1-b:3,4-b′]dithiophenylene.
Examples of bivalent 5 to 18 membered aromatic heterocyclic residues are bivalent 5 to 14 membered aromatic heterocyclic residues.
The bivalent 5 to 14 membered, respectively, 5 to 18 membered aromatic heterocyclic residue can contain one or more heteroatoms which can independently be selected from the group consisting of nitrogen, oxygen, sulfur, phosphor, silicon and arsenic, preferably from the group consisting of nitrogen, silicon and sulfur.
Preferably, A¹and A²are S.
Preferably, E is selected from the group consisting of
More preferably, E is selected from the group consisting of
Most preferably, E is
Preferably, R¹and R²are the same or different and are H, halogen, —CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X¹—R⁶—, —X²—Ar¹—, —X²—Ar²—Ar¹, —X²—Ar²—R⁷or —X²—Ar²—Ar²—R⁷,

- wherein
- X¹at each occurrence is independently —O—, —[Z¹—O]_a—, [O—Z¹]_a—O, —S—, —[Z¹—S—]_a—, —[S—Z¹]_a—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR⁸—, C(O)S—, —C(O)—, —S(O)—, —NR⁸C(O)— or —NR⁸—,
  - wherein
  - Z¹at 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
  - R⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²—C_6-14-aryl,
    - wherein
    - Z²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
- R⁶at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
- X²at each occurrence is independently —Z³—O—Z⁴—, —Z³—S—Z⁴—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR⁹, —C(O)S—, —C(O)—, —S(O)—, —NR⁹C(O)—, —Z³—SiR⁹ ₂—Z⁴—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
  - wherein
  - Z³and Z⁴at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
  - R⁹at each occurrence is independently H, C_1-20-alkyl, or —Z⁵—C_6-14-aryl,
    - wherein
    - Z⁵at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
- Ar¹at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar²and Ar³at 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^bis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
- R⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl and C_1-20-alkoxy.
  More preferably, R¹and R²are the same or different and are H, halogen, —CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X¹—R⁶, —X²—Ar¹, —X²—Ar²—Ar¹, —X²—Ar²—R⁷or —X²—Ar²—Ar³—R⁷,
- wherein
- X¹at each occurrence is independently —O—, —[Z¹—O]_a—, —[O—Z¹]_a—O, —S—, —[Z¹—S]_a—, or —[S—Z¹]_a—S—,
  - wherein
  - Z¹at 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
- R⁶at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
- X²at each occurrence is independently —Z³—O—Z⁴—, —Z³—S—Z⁴—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
  - wherein
  - Z³and Z⁴at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- Ar¹at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar²and Ara 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^bis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
- R⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

Even more preferably, R¹and R²are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X¹—R⁶or —X²—Ar¹,

- wherein
- X¹at each occurrence is independently —[Z¹—O]_a—, —[Z¹—S]_a—, or —[S—Z¹]_a—S—,
  - wherein
  - Z¹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
  - a at each occurrence is independently an integer from 1 to 10 and
- R⁶at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
- X²at each occurrence is independently —Z³—O—Z⁴—, —Z³—S—Z⁴—, C_1-30-alkylene or C_1-30-haloalkylene,
  - wherein
  - Z³and Z⁴at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
- Ar¹at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy.

Most preferably, R¹and R²are the same or different and are C_1-30-alkyl, C_1-30-haloalkyl or —X²—Ar¹,

- wherein
- X²at each occurrence is independently C_1-30-alkylene or C_1-30-haloalkylene, and
- Ar¹at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy.

In particular, R¹and R²are the same or different and are C_1-30-alkyl, for example C_1-20-alkyl or C_1-6-alkyl, for example methyl or n-hexyl.
Preferably, R³is H, halogen, CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X⁴—R¹², —X⁵—Ar⁷, —X⁵—Ar⁹—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,

- wherein
- X⁴at each occurrence is independently —[Z⁹—O]_b—, —[Z⁹—S—]_b—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁴— or C(O)S—,
  - wherein
  - Z⁹at 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
    - R¹⁴at each occurrence is independently H, C_1-20-alkyl, or —Z¹⁰—C_6-14-aryl,
    - wherein
    - Z¹⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
- R¹²at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
- X⁵at each occurrence is independently —Z¹¹—O—Z¹², —Z¹¹—S—Z¹²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁵, —C(O)S—, —Z¹¹—SiR¹⁵ ₂—Z¹²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
  - wherein
  - Z¹¹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
  - Z¹²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
  - R¹⁵at each occurrence is independently H, C_1-20-alkyl, or —Z¹³—C_6-14-aryl,
    - wherein
    - Z¹³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
- Ar¹at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl and
- R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

More preferably, R³is H, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X⁴—R¹², —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,

- wherein
- X⁴at each occurrence is independently —[Z⁹—O]_b— or —[Z⁹—S—]_b—,
  - wherein
  - Z⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene, and
  - b at each occurrence is independently an integer from 1 to 10 and
- R¹²at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
- X⁵at each occurrence is independently —Z¹¹—O—Z¹², —Z¹¹—S—Z¹²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
  - wherein
  - Z¹¹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene, and
  - Z¹²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- Ar⁷at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
- R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

Most preferably, R³is —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,

- wherein
- X⁵at each occurrence is a covalent bond,
- Ar⁷at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
- R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

In particular, R³is —X⁵—Ar⁸—R¹³,

- wherein
- X⁵is a covalent bond,
- Ar⁸is C_6-14-arylene, for example phenylene, and
- R¹³is C_1-20-alkyl.

For example R³is
Preferably, G¹and G²are the same or different and are phenylene, such as
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of

- wherein
- M¹is S, O, NH or SiR^sR^s, preferably M¹is S or NH, more preferably M¹is S, wherein R^sis hydrogen or C_1-30-alkyl,
  which phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents Rⁱ, wherein each Rⁱis independently selected from the group consisting of —CN, C_1-30-alkyl, —Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
  wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R, wherein each R is independently selected from the group consisting of halogen, —CN, *═O, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_m—C_1-20-alkyl, —S(O)_m—OC_1-20-alkyl, —S(O)_m—OC_1-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_mNH₂, —S(O)_mNH(C_1-20-alkyl), —S(O)_mN(C_1-20-alkyl)₂, —S(O)_mNH(C_6-14-aryl), —S(O)_mN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_mN(C_6-14-aryl)₂and Si(C_1-20-alkyl)₃, and
  wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, —S—C_1-20-alkyl, C_1-20-haloalkyl,
- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond, and
- m at each occurrence is independently 0, 1 or 2.

Preferably, each R is independently selected from the group consisting of C_1-30-alkyl, —Z¹⁷—O—C_3-10-alkyl, —Z¹⁷—S—C_3-10-cycloalkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond.

More preferably, each R is independently selected from the group consisting of C_1-30-alkyl and —Z¹⁷—C_6-14-aryl,
wherein C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O,

- wherein
- Z¹⁷at each occurrence is a covalent bond and C_6-14-aryl is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl and C_1-20-alkoxy.

Most preferably, each Rⁱis independently C_1-30-alkyl, preferably n-octyl, n-(2-ethyl)-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀), more preferably, n-dodecyl.
More preferably, G¹and G²are the same or different and are phenylene, such as
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of
which phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents Rⁱ, wherein each Rⁱis independently selected from the group consisting of C_1-30-alkyl, —Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_3-10-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

Most preferably, G¹and G²are the same or different and are a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue which monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue is
which monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue is substituted with 1 to 2 substituents R, wherein each R is independently selected from the group consisting of C_1-30-alkyl and —Z¹⁷—C_6-14-aryl,
wherein C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_6-14-aryl is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl and C_1-20-alkoxy,

- wherein
- Z¹⁷at each occurrence is a covalent bond.

In particular, G¹and G²are the same or different and are a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue which monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue is
which monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue is substituted with 1 substituent Rⁱ, wherein Rⁱis C_1-30-alkyl, preferably n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀), more preferably, n-dodecyl.
Preferably, L is C_6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein C_6-24-arylene and bivalent 5 to 18 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^l, wherein each R^lis independently selected from the group consisting of —CN, C_1-30-alkyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN, *═O, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_o—C_1-20-alkyl, —S(O)O—OC_1-20-alkyl, —S(O)_o—OC_6-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_oNH₂, —S(O)_oNH(C_1-20-alkyl), —S(O)_oN(C_1-20-alkyl)₂, —S(O)_oNH(C_6-14-aryl), —S(O)ON(C_1-20-alkyl)-C_6-14-aryl, —S(O)_oN(C_6-14-aryl)₂and Si(C_1-20-alkyl)₃, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, —S—C_1-20-alkyl, C_1-20-haloalkyl,

- wherein
- Z¹⁸at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond, and
- o at each occurrence is independently 0, 1 or 2,
  or

L is

- wherein
- R²³and R²⁴are the same or different and are H, halogen, —CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,
  - wherein
  - X⁷at each occurrence is independently —O—, —[Z¹⁹—O]_o—, —[O—Z¹⁹]_o—O—, —S—, —[Z¹⁹—S]_o—, —[S—Z¹⁹]_o—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR²⁷—, C(O)S—, —C(O)—, —S(O)—, —NR²⁷C(O)— or —NR²⁷—,
    - wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
    - R²⁷at each occurrence is independently H, C_1-20-alkyl, or —Z²⁰—C_6-14-aryl,
      - wherein
      - Z²⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R²⁵at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR²⁸, —C(O)S—, —C(O)—, —S(O)—, —NR²⁸C(O)—, —NR²⁸—, —Z²¹—SiR²⁸ ₂—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R²⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²³—C_6-14-aryl,
      - wherein
      - Z²³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹⁴at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar¹⁴and Ar¹⁵at 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^p, wherein each R^pis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl and C_1-20-alkoxy.

Preferably, each R^l, is independently selected from the group consisting of C_1-30-alkyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁸at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond.

More preferably, each R^lis independently selected from the group consisting of C_1-30-alkyl and —Z¹⁸—C_6-14-aryl,
wherein C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_6-14-aryl is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl and C_1-20-alkoxy,

- wherein
- Z¹⁸at each occurrence is a covalent bond.

Most preferably, each R^lis independently C_1-30-alkyl, preferably n-octyl, n-(2-ethyl)-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀), more preferably, n-hexadecyl.
Preferably, R²³and R²⁴are the same or different and are H, halogen, —CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,

- wherein
- X⁷at each occurrence is independently —O—, —[Z¹⁹—O]_c—, —[O—Z¹⁹]_c, —O—, —S—, [Z¹⁹—S—]_c—, or —[S—Z¹⁹]_c—S—,
  - wherein
  - Z¹⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
  - c at each occurrence is independently an integer from 1 to 10 and
- R²⁵at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
- X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
  - wherein
  - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- Ar¹³at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar¹⁴and Ar¹⁵at 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^p, wherein each R^pis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
- R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

More preferably, R²³and R²⁴are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X⁷—R²⁵or —X⁸—Ar¹³,

- wherein
- X⁷at each occurrence is independently —[Z¹⁹—O]_c—, —[Z¹⁹—S—]_c—, or —[S—Z¹⁹]_c—S—,
  - wherein
  - Z¹⁹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
  - c at each occurrence is independently an integer from 1 to 10 and
- R²⁵at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
- X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene or C_1-30-haloalkylene,
  - wherein
  - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
- Ar¹³at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy.

Most preferably, R²³and R²⁴are the same or different and are H, C_1-30-alkyl or C_1-30-haloalkyl, in particular H.
More preferably, L is a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^l, wherein each R^lis independently selected from the group consisting of C_1-30-alkyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁸at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,
  or

L is

wherein
R²³and R²⁴are the same or different and are H, halogen, —CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,

- wherein
- X⁷at each occurrence is independently —O—, —[Z¹⁹—O]_c—, —[O—Z¹⁹]_c—, —O—, —S—, —[Z¹⁹—S]_c—, or —[S—Z¹⁹]_c—S—,
  - wherein
  - Z¹⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
  - c at each occurrence is independently an integer from 1 to 10 and
- R²⁵at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
- X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
  - wherein
  - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- Ar¹³at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
- Ar¹⁴and Ar¹⁵at 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^p, wherein each R^pis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
- R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

Even more preferably, L is a bivalent 5 to 18 membered aromatic heterocyclic residue selected from the group consisting of
wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^l, wherein each R^lR^lis independently selected from the group consisting of C_1-30-alkyl and —Z¹⁸—C_6-14-aryl,
wherein C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_6-14-aryl is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl and C_1-20-alkoxy,

- wherein
- Z¹⁸at each occurrence is a covalent bond,
- wherein,
- M¹, M²and M³can be the same or different and are S, O, NH or SiR^tR^t, preferably M¹, M²are S or NH, and M³is S, O, NH or SiR^tR^t, more preferably M¹and M²are S, and M³is NH or SiR^tR^t,
  - wherein R′ is H or C_1-30-alkyl,
    or

L is

- wherein
- R²³and R²⁴are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X⁷—R²⁵or —X⁸—Ar¹³,
  - wherein
  - X⁷at each occurrence is independently —[Z¹⁹—O]_c—, —[Z¹⁹—S—]_c—, or —[S—Z¹⁹]_c—S—,
    - wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
  - R²⁵at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene or C_1-30-haloalkylene,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
  - Ar¹³at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy.

Even more preferably,
L is a bivalent 5 to 18 membered aromatic heterocyclic residue selected from the group consisting of
wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R′, wherein each wherein each R^lR^lis independently selected from the group consisting of C_1-30-alkyl and —Z¹⁸—C_6-14-aryl,
wherein C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_6-14-aryl is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl and C_1-20-alkoxy,

- wherein
- Z¹⁸at each occurrence is a covalent bond,
- wherein R^tis hydrogen or C_1-30-alkyl,
  or

L is

- wherein
- R²³and R²⁴are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X⁷—R²⁵or —X⁸—Ar¹³,
  - wherein
  - X⁷at each occurrence is independently —[Z¹⁹—O]_c—, —[Z¹⁹—S—]_c—, or —[S—Z¹⁹]_c—S—, wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
  - R²⁵at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene or C_1-30-haloalkylene,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
  - Ar¹³at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy.

Most preferably,

L is

wherein each R^lis independently C_1-30-alkyl, preferably n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀), more preferably, n-hexadecyl,
or

L is

wherein
R²³and R²⁴are the same or different and are H, C_1-30-alkyl or C_1-30-haloalkyl, in particular H.
Preferably, q, r and s are 0 or 1, with the proviso that q, r and s are not all 0 at the same time.
Preferably, n is an integer from 1 to 5000, 1 to 1000, 1 to 100, 1 to 50 or from 1 to 30, for example n can be an integer from 2 to 5000, 2 to 1000, 2 to 50, 2 to 30. In some embodiments, n can be an integer from 4 to 1000, 4 to 100, 8 to 1000 or 8 to 100.
In one embodiment,

A¹and A²are S,

E is

- wherein
- R¹and R²are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X¹—R⁶or —X²—Ar¹,
  - wherein
  - X¹at each occurrence is independently —[Z¹—O]_a—, —[Z¹—S—]_a—, or —[S—Z¹]_a—S—,
    - wherein
    - Z¹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
    - a at each occurrence is independently an integer from 1 to 10 and
  - R⁶at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
  - X²at each occurrence is independently —Z³—O—Z⁴—, —Z³—S—Z⁴—, C_1-30-alkylene or C_1-30-haloalkylene,
    - wherein
    - Z³and Z⁴at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
  - Ar¹at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy.

L is a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^l, wherein each R^lis independently selected from the group consisting of C_1-30-alkyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁸at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,
  q and s are 0,
  r is 1,
  and
  n is an integer from 1 to 1000, preferably 4 to 100.

In a second embodiment,

A¹and A²are S,

E is

- wherein
- R¹and R²are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X¹—R⁶or —X²—Ar¹,
  - wherein
  - X¹at each occurrence is independently —[Z¹—O]_a—, —[Z¹—S]_a—, or —[S—Z¹]_a—S—,
    - wherein
    - Z¹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
    - a at each occurrence is independently an integer from 1 to 10 and
  - R⁶at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
  - X²at each occurrence is independently —Z³—O—Z⁴—, —Z³—S—Z⁴—, C_1-30-alkylene or C_1-30-haloalkylene,
    - wherein
    - Z³and Z⁴at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
  - Ar¹at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy,

G¹and G²are the same or different and are phenylene such as
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of
which phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents Rⁱ, wherein each Rⁱis independently selected from the group consisting of C_1-30-alkyl, —Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

L is

- wherein
- R²³and R²⁴are the same or different and are H, C_1-30-alkyl, C_1-30-haloalkyl, —X⁷—R²⁵or —X⁸—Ar¹³,
  - wherein
  - X⁷at each occurrence is independently —[Z¹⁹—O]_c—, —[Z¹⁹—S—]_c—, or —[S—Z¹⁹]_c—S—,
    - wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
  - R²⁵at each occurrence is independently C_1-30-alkyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently C_1-30-alkylene or C_1-30-haloalkylene,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene or C_1-6-haloalkylene, and
  - Ar¹³at each occurrence is independently C_6-14-aryl, optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen C_1-6-alkyl and C_1-6-alkoxy,
    q and s are 1,
    r is 1,
    and
    n is an integer from 1 to 1000, preferably from 2 to 50.

In a third embodiment,

A¹and A²are S,

E is

G¹and G²are the same or different and are phenylene such as
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of
which phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents Rⁱ, wherein each Rⁱis independently selected from the group consisting of C_1-30-alkyl, —Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷C_3-10-cycloalkyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,
  q and s are 1,
  r is 0,
  and
  n is an integer from 1 to 1000, preferably from 1 to 30.

In a fourth embodiment,

A¹and A²are S,

E is

- wherein
- R³is —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,
  - wherein
  - X⁵at each occurrence is a covalent bond,
  - Ar⁷at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
    G¹and G²are the same or different and are phenylene such as

or, preferably, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of
which phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents R, wherein each R is independently selected from the group consisting of C_1-30-alkyl, —Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN and *═O, and
wherein C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,

L is

Examples of compounds, oligomers or polymers of formula 1 are
wherein n is an integer from 1 to 1000, preferably 1 to 100, 1 to 50 or from 1 to 30, for example n can be an integer from 2 to 1000, 2 to 100, 2 to 50, 2 to 30, or an integer from 4 to 100 or 8 to 100.
Also part of the present invention is a process for the preparation of the compound, oligomer or polymer of formula

- wherein
- A¹and A²can be the same or different and are S or Se,
- E is selected from the group consisting of

- wherein
- R¹and R²can 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, —X¹—R⁶, —X²—Ar¹, —X²—Ar²—Ar¹, —X²—Ar²—R⁷or —X²—Ar²—Ar³—R⁷,
  - wherein
  - X¹at each occurrence is independently —O—, —[Z¹—O]_a—, [O—Z¹]_a—, —O—, —S—, —[Z¹—S—]_a—, —[S—Z¹]_a—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR⁸, C(O)S—, —C(O)—, —S(O)—, —NR⁸C(O)— or —NR⁸—,
    - wherein
    - Z¹at 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
    - R⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²—C_6-14-aryl,
      - wherein
      - Z²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R⁶at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X²at each occurrence is independently —Z³—O—Z⁴—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR⁹, —C(O)S—, —O(CO)—, —S(CO)—, —NR⁹C(O)—, —NR⁹—, —Z³—SiR⁹ ₂—Z⁴—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z³and Z⁴at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R⁹at each occurrence is independently H, C_1-20-alkyl, or —Z⁵—C_6-14-aryl,
      - wherein
      - Z⁵at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^a, wherein each R^ais independently selected from the group consisting of halogen, CN, 016 alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar²and Ar³at 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^bis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X³—Ar⁴, —X³—Ar⁵—Ar⁴, —X³—Ar⁵—R¹⁰, or —X³—Ar⁵—Ar⁶—R¹⁰,
    - wherein
    - X³at each occurrence is independently —Z⁶—O—Z⁷—, —Z⁶—S—Z⁷, —S(O)—, —C(O)—, —C(O)O—, —(O)NR¹¹, —C(O)S—, —O(CO)—, —S(CO)—, —NR¹¹C(O)—, —NR¹¹—, —Z⁶—SiR¹¹ ₂—Z⁷—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z⁶and Z⁷at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R¹¹at each occurrence is independently H, C_1-20-alkyl or —Z⁸—C_6-14-aryl,
      - wherein
      - Z⁸at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
    - Ar⁴at 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^cis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
    - Ar⁵and Ar⁶at 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^dis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
    - R¹⁰at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
  - R³, R⁴and R⁵can 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, —X⁴—R¹², —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,
    - wherein
    - X⁴at each occurrence is independently —[Z⁹—O]_b—, —[Z⁹—S—]_b—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁴— or C(O)S—,
      - wherein
      - Z⁹at 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
      - R¹⁴at each occurrence is independently H, C_1-20-alkyl, or —Z¹⁰—C_6-14-aryl,
      - wherein
      - Z¹⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R¹²at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁵at each occurrence is independently —Z¹¹—O—Z¹², —Z¹¹—S—Z¹²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁵, —C(O)S—, —Z¹¹—SiR¹⁵ ₂—Z¹²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z¹¹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - Z¹²at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R¹⁵at each occurrence is independently H, C_1-20-alkyl, or —Z¹³—C_6-14-aryl,
      - wherein
      - Z¹³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar⁷at 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^eis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar⁸and Ar⁹at 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^fis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl and
  - R¹³at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁶—Ar¹⁰, —X⁶—Ar¹¹—Ar¹⁰, —X⁶—Ar¹¹—R¹⁶, or —X⁶—Ar¹¹—Ar¹²—R¹⁷,
    - wherein
    - X⁶at each occurrence is independently —Z¹⁴—O—Z¹⁵, —Z¹⁴—S—Z¹⁵, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁸, —C(O)S—, —O(CO)—, —S(CO)—, —NR¹⁸C(O)—, —NR¹⁸—, —Z¹⁴—SiR¹⁸ ₂—Z¹⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z¹⁴and Z¹⁵at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R¹⁸at each occurrence is independently H, C_1-20-alkyl or —Z¹⁶—C_6-14-aryl,
      - wherein
      - Z¹⁶at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹⁰at 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^g, wherein each R^gis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar¹¹and Ar¹²at 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^h, wherein each R^his independently selected from the group consisting of halogen, CN, C_1-6-alkoxy and C_1-6-haloalkyl and
  - R¹⁷at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
- R¹⁹is O or C(CN)₂, and
- R²⁰and R²¹are the same or different and are R²²or CN,
- wherein R²²has the same meaning as R¹,

G¹and G²are the same or different and are phenylene or a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, which phenylene and monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents Rⁱ, wherein each Rⁱis independently selected from the group consisting of halogen, —CN, —NO₂, OH, C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, —Z¹⁷—O—C_1-30-alkyl, —Z¹⁷—S—C_1-30-alkyl, —Z¹⁷—C_3-10-cycloalkyl, —Z¹⁷—C_5-10-cycloalkenyl, —Z¹⁷—C_8-10-cycloalkynyl, —Z¹⁷—C_6-14-aryl, —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_5-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^j, wherein each R^jis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, —OH, —NH₂, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_mH, —S(O)₂OH, —S(O)_m—OC_1-20-alkyl, —S(O)_m—OC_6-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)OH, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_mNH₂, —S(O)_mNH(C_1-20-alkyl), —S(O)_mN(C_1-20-alkyl)₂, —S(O)_mNH(C_6-14-aryl), —S(O)_mN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_mN(C_6-14-aryl)₂, SiH₃, SiH(C_1-20-alkyl)₂, SiH₂(C_1-20-alkyl) and Si(C_1-20-alkyl)₃, and
wherein C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein each R^kis independently selected from the group consisting of C_1-20-alkyl, C_2-20-alkenyl, C_2-20-alkynyl, C_1-20-alkoxy, C_1-20-haloalkyl,

- wherein
- Z¹⁷at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- m at each occurrence is independently 0, 1 or 2,

L is C_6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein C_6-24-arylene and bivalent 5 to 18 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^l, wherein each R^lis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, OH, *═O(C_1-30-alkyl)₂, C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, —Z¹⁸—O—C_1-30-alkyl, —Z¹⁸—S—C_1-30-alkyl, —Z¹⁸—C_3-10-cycloalkyl, —Z¹⁸—C_5-10-cycloalkenyl, —Z¹⁸—C_8-10-cycloalkynyl, —Z¹⁸—C_6-14-aryl, —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,
wherein C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_6-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein each R^mis independently selected from the group consisting of halogen, —CN, —NO₂, *═O, —OH, —NH₂, —NH(C_1-20-alkyl), —N(C_1-20-alkyl)₂, —N(C_1-20-alkyl)-C_6-14-aryl, —N(C_6-14-aryl)₂, —S(O)_oH, —S(O)_o—C_1-20-alkyl, —S(O)₂OH, —S(O)_o—OC_1-20-alkyl, —S(O)_o—OC_6-14-aryl, —CHO, —C(O)—C_1-20-alkyl, —C(O)—C_6-14-aryl, —C(O)OH, —C(O)—OC_1-20-alkyl, —C(O)—OC_6-14-aryl, —C(O)NH₂, —C(O)NH—C_1-20-alkyl, —C(O)N(C_1-20-alkyl)₂, —C(O)NH—C_6-14-aryl, —C(O)N(C_1-20-alkyl)-C_6-14-aryl, —C(O)N(C_6-14-aryl)₂, —C(S)NH₂, —C(S)NH—C_1-20-alkyl, —C(S)N(C_1-20-alkyl)₂, —C(S)N(C_6-14-aryl)₂, —C(S)N(C_1-20-alkyl)-C_6-14-aryl, —C(S)NH—C_6-14-aryl, —S(O)_oNH₂, —S(O)ONH(C_1-20-alkyl), —S(O)_oN(C_1-20-alkyl)₂, —S(O)ONH(C_6-14-aryl), —S(O)_oN(C_1-20-alkyl)-C_6-14-aryl, —S(O)_oN(C_6-14-aryl)₂, SiH₃, SiH(C_1-20-alkyl)₂, SiH₂(C_1-20-alkyl) and Si(C_1-20-alkyl)₃, and
wherein C_3-10-cycloalkyl, C_6-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein each Rⁿis independently selected from the group consisting of C_1-20-alkyl, C_2-20-alkenyl, C_2-20-alkynyl, C_1-20-alkoxy, —S—C_1-20-alkyl, C_1-20-haloalkyl,

- wherein
- Z¹⁸at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
- o at each occurrence is independently 0, 1 or 2,
  or

L is

- wherein
- R²³and R²⁴can 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, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,
  - wherein
  - X⁷at each occurrence is independently —O—, —[Z¹⁹—O]_c—, —[O—Z¹⁹]_c—, —O—, —S—, —[Z¹⁹—S—]_c—, —[S—Z¹⁹]_c—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR²⁷—, C(O)S—, —C(O)—, —S(O)—, —NR²⁷C(O)— or —NR²⁷—,
    - wherein
    - Z¹⁹at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,
    - c at each occurrence is independently an integer from 1 to 10 and
    - R²⁷at each occurrence is independently H, C_1-20-alkyl, or —Z²⁰—C_6-14-aryl,
      - wherein
      - Z²⁰at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - R²⁵at each occurrence is independently C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,
  - X⁸at each occurrence is independently —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR²⁸, —C(O)S—, —O(CO)—, —S(CO)—, —NR²⁸C(O)—, —NR²⁸—, —Z²¹—SiR²⁸ ₂—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
    - wherein
    - Z²¹and Z²²at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
    - R²⁸at each occurrence is independently H, C_1-20-alkyl, or —Z²³—C_6-14-aryl,
      - wherein
      - Z²³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹²at each occurrence is independently C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein each R^ois independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar¹⁴and Ar¹⁵at 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^p, wherein each R^pis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁹—Ar¹⁶, —X⁹—Ar¹⁷—Ar¹⁶, —X⁹—Ar¹⁷—R²⁹, or —X⁹—Ar¹⁷—Ar¹⁸—R²⁹,
    - wherein
    - X⁹at each occurrence is independently —Z²⁴—O—Z²⁵—, —Z²⁴—S—Z²⁵, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR³⁰, —C(O)S—, —O(CO)—, —S(CO)—, —NR³⁰C(O)—, —NR³⁰—, —Z²⁴—SiR³⁰ ₂—Z²⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,
      - wherein
      - Z²⁴and Z²⁵at each occurrence are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and
      - R³⁰at each occurrence is independently H, C_1-20-alkyl or —Z²⁶—C_6-14-aryl,
      - wherein
      - Z²⁶at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,
  - Ar¹⁶at 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^q, wherein each R^qis independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl,
  - Ar¹⁷and Ar¹⁸at 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^r, wherein each R^ris independently selected from the group consisting of halogen, CN, C_1-6-alkyl, C_1-6-alkoxy and C_1-6-haloalkyl, and
  - R²⁶at each occurrence is independently C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,
    q and s are the same or different and are 0, 1, 2, 3, 4 or 5,
    r is 0, 1 or 2,
    and
    n is an integer from 1 to 10'000,
    which process comprises,
    preferably, (i) the step of reacting a compound of formula

wherein A¹, A²and E are as defined above, and Hal is halogen, preferably —Br,
with a compound of formula
wherein G¹, G², L, q, r, and s are as defined above, and R³¹, R³², R³³, R³⁴, R³⁵and R³⁶are the same and are C_1-30-alkyl, preferably C_1-6-alkyl, most preferably n-butyl or methyl,
in the presence of a metal catalyst,
or
(ii) the step of reacting a compound of formula
wherein A¹, A²and E, G¹, G², r and s are as defined above, and Hal is halogen, preferably —Br,
with a compound of formula
wherein L and r are as defined above, and R³¹, R³², R³³, R³⁴, R³⁵and R³⁶are the same and are C_1-30-alkyl, preferably C_1-6-alkyl, most preferably n-butyl or methyl,
in the presence of a metal catalyst,
or
(iii) the step of reacting a compound of formula
wherein A¹, A²and E are as defined above, and R³¹, R³², R³³, R³⁴, R³⁵and R³⁶are the same and are C_1-30-alkyl, preferably C_1-6-alkyl, most preferably n-butyl or methyl,
with a compound of formula
wherein G¹, G², L, q, r, and s are as defined above, and Hal is halogen, preferably —Br,
in the presence of a metal catalyst,
or
(iv) the step of reacting a compound of formula
wherein A¹, A², E, G¹, G², r and s are as defined above, and R³¹, R³², R³³, R³⁴, R³⁵and R³⁶are the same and are C_1-30-alkyl, preferably C_1-6-alkyl, most preferably n-butyl or methyl,
with a compound of formula
wherein L and r are as defined above, and Hal is halogen, preferably —Br,
in the presence of a metal catalyst.
Preferably R³¹, R³², R³³, R³⁴, R³⁵and R³⁶are methyl or n-butyl.
The metal catalyst is preferably a palladium catalyst such tris(dibenzylideneacetone)-dipalladium(0), preferably in combination with a phosphine such as tri-o-tolylphosphine. The reaction is preferably performed at elevated temperatures such 80 to 200° C., preferably 90 to 150° C. The reaction can be performed in an inert organic solvent such as chlorobenzene. The reaction can be stopped by the addition of end cappers such as 2-bromothiophene and 2-tributylstannylthiophene. The crude product may be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, for example with acetone.
Alternatively, the compound, oligomer or polymer of formula
wherein A¹, A², E, G¹, L, G², q, r, s and n are as defined above,
can be prepared by the process as outlined above but using
wherein G¹, G², L, q, r, and s are as defined above, and R³⁷, R³⁸, R³⁹and R⁴⁰are the same and are H or C_1-30-alkyl, or R³⁷and R³⁸, respectively, R³⁹and R⁴⁰form together with —O—B—O— a 5 to 8-membered cyclic ring, for example a pinacol type ring of formula
instead of the compound of formula 3,
wherein L and r are as defined above, and R³⁷, R³⁸, R³⁹and R⁴⁰are the same and are H or C_1-30-alkyl, or R³⁷and R³⁸, respectively, R³⁹and R⁴⁰form together with —O—B—O— a 5 to 8-membered cyclic ring, for example a pinacol type ring of formula
instead of the compound of formula 9,
wherein A¹, A²and E are as defined above, and R³⁷, R³⁸, R³⁹and R⁴⁰are the same and are H or C_1-30-alkyl, or R³⁷and R³⁸, respectively, R³⁹and R⁴⁰form together with —O—B—O— a 5 to 8-membered cyclic ring, for example a pinacol type ring of formula
instead of the compound of formula 10, or
wherein A¹, A², E, G¹, G², r and s are as defined above, and R³⁷, R³⁸, R³⁹and R⁴⁰are the same and are H or C_1-30-alkyl, or R³⁷and R³⁸, respectively, R³⁹and R⁴⁰form together with —O—B—O— a 5 to 8-membered cyclic ring, for example a pinacol type ring of formula
instead of the compound of formula 12.
The compound of formula
wherein A¹and A²are as defined above, and Hal is halogen, preferably —Br,

and E is

wherein R¹, R²and R³are as defined above,
can be prepared by a process, which comprises the step of reacting a compound of formula
wherein A¹, A²and E are as defined above, and R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl,
with a halogenating agent in the presence of an acidic catalyst.
The halogenating agent is preferably Br₂. The acidic catalyst is preferably trichloroacetic acid. The reaction is preferably carried out in an inert organic solvent such as chloroform. The reaction is preferably carried out at ambient temperature, for example at a temperature from 15 to 30° C., more preferably at a temperature from 18 to 26° C. The reaction mixture can be worked up by conventional methods.
The compound of formula
wherein A¹, A²and E are as defined above, and R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl,
can be prepared by a process, which comprises the step of coupling a compound of formula
wherein A¹, A², R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are as defined above, and Hal is halogen, preferably —Br,
with H-E-H or
wherein R⁴⁷, R⁴⁸, R⁴⁹and R⁵⁰are the same and are H or C_1-30-alkyl, or R⁴⁷and R⁴⁸, respectively, R⁴⁹and R⁵⁰form together with —O—B—O— a 5 to 8-membered cyclic ring, for example a pinacol type ring of formula.
in the presence of a metal catalyst.
The metal catalyst can be a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0), or tris(dibenzylideneacetone)dipalladium(0) in combination with a phosphine such as rac-BI NAP or tri-tert-butylphosphine. Preferably, the reaction is carried out in the presence of a base such as potassium carbonate or sodium tertbutoxide. The reaction can be carried out in an inert organic solvent such as toluene, or in mixtures of inert organic solvents and water, for example in mixtures of toluene and water. The reaction can be carried out at elevated temperatures, for example at a temperature from 70 to 200° C., preferably at a temperature from 80 to 150° C. The reaction mixture can be worked up by conventional methods.
If E is
the vic-bis(pinacolatoboryl) complex
is preferably used in the reaction.
This vic-bis(pinacolatoboryl) complex can be synthesized via platinum catalyzed boronation of
The compound of formula
wherein A¹and A²are as defined above, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably, C_1-20-alkyl, preferably C_1-6-alkyl, more preferably isopropyl, and Hal is halogen, preferably —Br,
can be prepared by a process which comprises the step of reacting
wherein A¹and A²are as defined above, and Hal is halogen, preferably —Br,
with R⁴¹R⁴²R⁴³Si—Hal and R⁴⁴R⁴⁵R⁴⁶Si—Hal and a base, wherein R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are as defined above, and Hal is halogen, preferably —Br.
An example of a base is lithium diisopropylamide. The reaction can be performed in an inert organic solvent, for example THF. The reaction can be performed at a temperature of 0 to −100° C., preferably at −40 to −90° C., preferably at around −78° C. The reaction mixture obtained can be worked-up by conventional methods.
The compound of formula
wherein A¹and A²are as defined above, and Hal is halogen, preferably —Br,
can be prepared by a process comprising the step of reacting
wherein A¹and A²are as defined above,
with a halogenating agent.
An example of a halogenating agent is N-bromosuccinimide. The reaction can be performed in an inert organic solvent, for example DMF. The reaction can be performed at elevated temperature, for example at a temperature from 20 to 100° C., preferably at 40 to 80° C. The reaction mixture obtained can be worked-up by conventional methods.
A compound of formula 2d can also be prepared via thiocyanation of 2,6-diamino-benzothiazole 18 as reported by Landquist, J. K. J. Chem. Soc. C 1967, 2212 to 2220, followed by Sandmeyer reaction as depicted below
A compound of formula 2e can also be prepared via condensation of 3,6-diamino-1,2-phenylene dihydrogen thiosulphate 19 with thiophene-2-carboxylic acid in analogy to the processes described by Green, A. G. J. Chem. Soc., Trans. 1903, 83, 1201 to 1212, and by Cox, R. J.; Clecak, N. J. J. Org. Chem. 1968, 33, 2132 to 2133, followed by halogenation as depicted below
The compound of formula
wherein A¹and A²are as defined above, and Hal is halogen, preferably —Br,
and E is selected from the group consisting of
wherein R⁴, R⁵, R¹⁹, R²⁰and R²¹are as defined above,
can be prepared by a process, which comprises the step of reacting a compound of formula
wherein A¹and A²are as defined above, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl, and Hal is halogen, preferably —Br,
with a suitable compound to incorporate E,
in the presence of a base such as butyl lithium.
For example, the compounds of formulae 2f, 2g, 2h and 2i can be prepared as follows:
The compound of formula
wherein A¹and A²are as defined above, and Hal is halogen, preferably —Br,
and E is selected from the group consisting of
wherein R⁴, R⁵, R¹⁹, R²⁰and R²¹are as defined above,
can also be prepared by a process, which comprises the step of reacting a compound of formula
wherein A¹and A²are as defined above, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl,
with a suitable compound to incorporate E,
in the presence of a base such as lithium diisopropylamide, for example as described for similar compounds in WO 2009/069687.
The compound of formula
wherein A¹and A²are as defined above, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl,
can be prepared via oxidative coupling of
For example the compound of formula 20a can be prepared as follows:
The compound of formula
wherein
A¹and A²can be the same or different and are S or Se,
E is selected from the group consisting of
wherein
R¹, R², R³, R⁴, R⁵, R¹⁹, R²⁰and R²¹are as defined above,
G¹and G²are are as defined above,
q and s are as defined above, and
Hal is halogen,
can be prepared by reacting the compound of formula
wherein A¹and A²are as defined above, and Hal is halogen,
with suitable compounds to incorporate G¹and G², such as stannyl functionalized G¹and G²or borate functionalized G¹or G²or Grignard functionalized G¹and G², in the presence of a metal catalyst,
followed by halogenation.
For example, the compound of formula 8a can be prepared as follows:
Also part of the invention is the compound of formula
wherein
A¹and A²can be the same or different and are S or Se,
E is selected from the group consisting of
wherein
R¹, R², R³, R⁴, R⁵, R¹⁹, R²⁰and R²¹are as defined above
and Hal is halogen.
Also part of the invention is the compound of formula
wherein
A¹and A²can be the same or different and are S or Se,

E is

and R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl.
Also part of the invention is a compound of formula
wherein A¹and A²can be the same or different and are S or Se,
R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵and R⁴⁶are C_1-30-alkyl, preferably C_1-6-alkyl, more preferably isopropyl, and Hal is halogen, preferably —Br.
Also part of the present invention is an electronic device comprising the compounds, oligomers and polymers of the present invention.
The electronic device can be any electronic device, for example an organic photovoltaic (OPV) cell, an organic field-effect transistor (OFET) or an organic light emitting diode (OLED). Preferably, it is an organic field-effect transistor.
The organc field effect transistor comprising the compounds, oligomers and polymers of the present invention can be prepared by solution deposition of a solution of the compounds, oligomers and polymers of the present invention in a suitable solvent. The solvent can be an organic solvent, for example 1,2-dichlorobenzene. Solution deposition can be performed by methods known in the art, for example by spin coating, for example at 2000 rpm, 255 acc (acc: spin acceleration), 1 minute.
The organic field effect transistor can have any architecture known in the art, for example a bottom gate bottom contact (BGBC) architecture as depicted in FIG. 1. When the organic field effect transistor has a bottom gate bottom contact (BGBC) architecture, the substrate (or gate electrode), the gate dielectric, and the source and drain electrodes can be any substrate, gate dielectric, source and drain electrode known in the art. For example, the substrate (or gate electrode) can be heavily doped silicon wafer, the gate dielectric can be thermally grown silica, and the source and drain electrode can be made of gold which is lithographically patterned. Before deposition of the compounds, oligomers and polymers of the present invention as semiconductors, the device can be vapor treated with hexamethyldisilazane (HMDS).
Also part of the invention is the use of the compound, oligomer or polymer of the present invention as organic semiconducting material.
The compounds, oligomers and polymers of the present invention show a surprising high ioniziation potential, which may contribute to better ambient oxidative stability. The compounds, oligomers and polymers of the present invention are compatible with liquid processing techniques and are suitable for use as semiconductors in organic field effect transistors. The organic field effect transistor using the compounds, oligomers and polymers of the present invention as semiconductors show good field-effect mobilities and on/off ratios.

FIG. 1 shows an organic field effect transistor having a bottom gate bottom contact (BGBC) architecture.

EXAMPLES

Example 1

Preparation of 2,2′-dibromo-(5,6-dihexylbenzo[2,1-d;3,4-d′]bisthiazole) (2a)

Preparation of 4,4′-dibromo-5,5′-bithiazole (6a)

N-bromosuccinimide (6.35 g, 35.66 mmol, 4 eq.) is added to a stirred homogeneous solution of 5,5′-bithiazole (7a) (1.5 g, 8.9 mmol) in anhydrous DMF (125 mL). The reaction mixture is heated at 60° C. for 3 hours. The reaction mixture is washed subsequently with an aqueous solution of 10% sodium bicarbonate (200 mL), extracted with dichloromethane (200 mL), washed with water (3×100 mL) and sodium chloride saturated water (100 mL), and dried over anhydrous sodium sulfate. The crude product is re-crystallized from dichloromethane/n-hexane (1:10). Yellowish crystals are obtained. ¹H-NMR (d-chloroform) (400 MHz): δ 8.87 (s, 2H). ¹³C-NMR (d-chloroform) (400 MHz): δ 154.8, 129.3, 122.5.

Preparation of 2,2′-bis(triisopropylsilyl)-4,4′-dibromo-5,5′-bithiazole (5a)

1.84 mL of a 2M solution of lithium diisopropylamide (0.39 g, 3.68 mmol, 2.4 eq.) in THF is added dropwise to a solution of 4,4′-dibromo-5,5′-bithiazoles (6a) (0.5 g, 1.53 mmol) in anhydrous THF (20 mL) at −78° C. over 10 minutes. The reaction mixture is allowed to stir for 3 hours, and then triisopropylsilyl chloride (0.709 g, 0.79 mL, 3.68 mmol, 2.4 eq.) is added slowly. The reaction mixture is warmed up to room temperature overnight. The reaction mixture is diluted with ethyl acetate (140 mL), and the organic layer is washed with sodium bicarbonate saturated water (70 mL) and sodium chloride saturated water (70 mL), dried over magnesium sulfate and concentrated in vacuo. Column chromatography using gradient solvent from n-hexane to ethyl acetate/n-hexane (5/95) provides a yellow solid. ¹H-NMR (d-chloroform) (400 MHz): δ 2.43-1.5 (m, J=8 Hz, 6H), δ 1.16-1.18 (d, J=7.6 Hz, 36H). ¹³C-NMR (d-chloroform) (400 MHz): δ 172.7, 130.5, 125.1, 18.7, 11.8.

Preparation of 2,2′-bis(triisopropylsilyl)-(5,6-dihexylbenzo[2,1-d;3,4-d′]bisthiazole) (4a)

A mixture of 5a (0.5 g, 0.783 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.090 g, 0.078 mmol, 0.1 eq.) is degassed 3 times. A solution of vic-bis(pinacolatoboryl)-7-tetradecene (0.456 g, 1.018 mmol, 1.3 eq.), in anhydrous toluene (5 mL) is added, followed by 12 mL of toluene (total 17 mL anhydrous toluene). Subsequently 2.8 mL of degassed aqueous solution of potassium carbonate (0.64 g, 4.70 mmol, 6 eq.) is added. The reaction mixture is stirred and heated at 100° C. overnight. The reaction mixture is allowed to cool to room temperature, and is diluted with ethyl acetate (50 mL). The resulting reaction mixture is washed with ammonium chloride saturated water (50 mL) and the aqueous layer is extracted with ethyl acetate (3×50 mL). The combined organic layers are washed with sodium chloride saturated water (25 mL), dried over magnesium sulfate, and concentrated in vacuo. Column chromatography using a gradient solvent from n-hexane to ethyl acetate/n-hexane (10/90) provides an off-white solid. ¹H-NMR (d-chloroform) (400 MHz): δ 3.37 (dd, J=8 Hz, 4H), δ 1.74-1.76 (m, J=8 Hz, 4H), δ 1.47-1.55 (m, J=8 Hz, 6H), δ 1.33-1.37 (m, J=8 Hz, 12H), δ 1.2-1.22 (d, J=8 Hz, 36H), δ 0.87-0.92 (t, J=7.6 Hz, 6H). LC-MS: 95% purity with m/z 673.4.

A solution of bromine (0.34 g, 0.11 mL, 2.11 mmol, 4 eq.) in chloroform (5 mL) containing trichloroacetic acid (7 mg) is added dropwise and slowly to a solution of 4a (0.355 g, 0.527 mmol) in chloroform (8 mL) at 0° C. The reaction mixture is stirred at room temperature for 3 days. The reaction mixture is diluted with dichloromethane (50 mL), washed with an aqueous solution of 20 weight % sodium thiosulfate (50 mL) and with an aqueous solution of 10 weight % sodium bicarbonate (50 mL). Subsequently the organic layer is dried over magnesium sulfate and concentrated in vacuo. Purification by column chromatography (ethyl acetate/n-hexane (10/90)) followed by re-crystallisation from ethanol affords light brown crystals. ¹H-NMR (d-chloroform) (400 MHz): δ 3.17 (dd, J=8 Hz, 4H), δ 1.66 (m, J=8 Hz, 4H), δ 1.47 (m, J=8 Hz, 4H), δ 1.35 (m, J=8 Hz, 8H), δ 0.92 (t, J=7.6 Hz, 6H). LC-MS: 98% purity with m/z 519. Elemental analysis (calcd): C, 46.34 (46.36); H, 5.06 (5.09).

Example 2

Preparation of poly(benzobisthiazole-cyclopentadithiophene) (1a)

Dibromo-benzobisthiazole (2a) (60 mg, 0.116 mmol, 1 eq.), bis(trimethylstannyl)-cyclopentadithiophene (3a) (110 mg, 0.116 mmol, 1 eq.), tris(dibenzylidene-acetone)dipalladium(0) (3.2 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (2.1 mg, 0.007 mmol, 6% eq.) are added into a Schlenk flask and degassed 3 times. Chlorobenzene (4 mL) is added and the reaction mixture is stirred at 100° C. overnight then at 130° C. for 2 days. 2-Bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL) are added as end cappers, with 2-bromothiophene added first followed by 2-tributylstannylthiophene 2 hours later. After another 2 hours stirring, the reaction mixture is cooled to room temperature. The reaction mixture is then added dropwise to methanol (200 mL), filtered, and then subjected to Soxhlet extraction with acetone. The polymer is recovered as solid mass and showed Mn=8360 g/mol (Mw=24264 g/mol & PDI=2.92). Elemental analysis (calcd): C, 70.77 (74.48); H, 8.93 (9.63).

Example 3

Preparation of poly(benzobisthiazole-bisthienylethylene) (1b)

Dibromo-benzobisthiazole (2a) (55 mg, 0.106 mmol, 1 eq.) prepared as described in example 1, bis(2-trimethylstannyl-4-dodecylthienyl)ethylene (3b) (90.7 mg, 0.106 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (2.9 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (1.9 mg, 0.006 mmol, 6% eq.) are added into a Schlenk flask and degassed 3 times. Chlorobenzene (2 mL) is added and the reaction mixture is stirred at 130° C. for 2 days. 2-Bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL) are added as end cappers, with 2-bromothiophene added first followed by 2-tributylstannylthiophene 2 hours later. After another 2 hours stirring, the reaction mixture is cooled to room temperature. The mixture is filtered and the filtrate is concentrated and added dropwise to methanol (200 mL), filtered, and then subjected to Soxhlet extraction with acetone. The polymer is recovered as solid mass and showed Mn=3368 g/mol (Mw=4749 g/mol & D=1.41).

Example 4

Preparation of poly(benzobisthiazole-bithiophene) (1c)

Preparation of 2,2′-dibromo-(5,6-dimethylbenzo[2,1-d;3,4-d′]bisthiazole) (2b)

Dibromo-benzobisthiazole (2b) is prepared in analogy to 2,2′-dibromo-(5,6-dihexyl-benzo[2,1-d;3,4-d′]bisthiazole) (2a) in example 1, except that vic-bis(pinacolatoboryl)-2-butene (with the equivalent of 1.3 eq to the substrate 5a) is used instead of vic-bis-(pinacolatoboryl)-7-tetradecene (with the equivalent of 1.3 eq to the substrate 5a).

Preparation of poly(benzobisthiazole-bithiophene) (1c)

Dibromo-benzobisthiazole (2b) (79 mg, 0.209 mmol, 1 eq.) is added as a 4.2 mL chlorobenzene solution into a pre-degassed mixture of bis(2-trimethylstannyl-2-do-decylthiophene) (3c) (173.1 mg, 0.209 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.). The reaction mixture is stirred at 130° C. for 2 days. After two days of reaction, tris(dibenzylideneacetone)-dipalladium(0) (5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.) is added. After four days of reaction, another portion of tris(dibenzylidene-acetone)dipalladium(0) (5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.) is added. After total 6 days, the polymerization is stopped by the addition of 2-bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL). 2-Bromothiophene is added first followed by 2-tributylstannylthiophene 4 hours later. After another 24 hours stirring, the reaction mixture is cooled to room temperature. The mixture is filtered and the filtrate is concentrated and added dropwise to a methanolic solution of 5 weight % HCl (200 mL). The polymer is filtered and before soxhlet extraction in acetone showed Mn=959 g/mol (Mw=1410 g/mol & D=1.47).

Example 5

Preparation of N-4-decylaniline-2,6-dibromo dithiazolo[2,3-d;3′,2′-b]pyrrole (2c)

Preparation of N-4-decylaniline-2,6-bis(triisoproylsilyl) dithiazolo[2,3-d;3′,2′-b]pyrrole) (4b)

A mixture of bis(triisopropylsilyl)-dibromobithiazole (5a) (790 mg, 1.237 mmol), tris(dibenzylideneacetone)dipalladium(0) (113 mg, 0.123 mmol, 0.1 eq.), sodium tert-but-oxide (200 mg, 2.968 mmol, 2.4 eq.) and rac-BINAP (153 mg, 0.347 mmol, 0.2 eq.) is degassed 3 times. 4-n-Decylaniline (360 mg, 1.546 mmol, 1.25 eq.) in anhydrous toluene (18 mL) is added. The reaction mixture is stirred and heated at 100° C. for 2 days under nitrogen. After the mono-aminated intermediate is formed tris(dibenzylidene-acetone)dipalladium(0) (56 mg, 0.061 mmol, 0.05 eq.) and 0.36 mL of a 10 weight % solution of tri-tert-butylphosphine (24 mg, 0.173 mmol, 0.1 eq.) in n-hexane is added. The reaction mixture is stirred at 100° C. for 2 days under nitrogen. Afterwards the reaction mixture is diluted with ethyl acetate (100 mL). The resulting reaction mixture is washed with ammonium chloride saturated water (100 mL) and the aqueous layer is extracted with ethyl acetate (3×70 mL). The combined organic layers are washed with sodium chloride saturated water (50 mL), dried over magnesium sulfate, and concentrated in vacuo. Column chromatography using ethyl acetate/n-hexane (2/98) provided off-white solid. ¹H-NMR (d-chloroform) (400 MHz): δ 8.58 (d, J=9.6 Hz, 2H), δ 7.34 (d, J=8.4 Hz, 2H), δ 2.28 (dd, J=8 Hz, 2H), δ 1.65 (m, J=8 Hz, 2H), δ 1.52-1.46 (m, J=8 Hz, 6H), δ 1.27 (s, 14H), δ 1.19-1.21 (d, J=8 Hz, 36H), δ 0.88 (t, J=7.6 Hz, 3H).

A solution of bromine (0.16 g, 0.05 mL, 1.01 mmol, 4 eq.) in chloroform (3 mL) containing trichloroacetic acid (4 mg) is slowly and dropwise added to a solution of 4b (0.180 g, 0.253 mmol) in chloroform (4 mL) at 0° C. The reaction mixture is stirred at room temperature for 2 days. The reaction mixture is diluted with dichloromethane (50 mL), washed with an aqueous solution of 20 weight % sodium thiosulfate (50 mL) and an aqueous solution of 10 weight % sodium bicarbonate (50 mL). Subsequently the organic layer is dried over magnesium sulfate and concentrated in vacuo. Purification by column chromatography using n-hexane followed by re-crystallisation from n-hexane affords white flakes. ¹H-NMR (d-chloroform) (400 MHz): δ 7.88 (d, J=8.4 Hz, 2H), δ 7.35 (d, J=8 Hz, 2H), δ 2.66 (dd, J=7.6 Hz, 2H), δ 1.63 (m, J=7.6 Hz, 2H), δ 1.28 (s, 14H), δ 0.88 (t, J=7.6 Hz, 3H). LC-MS: 97.2% purity with m/z 556. Elemental analysis (calcd): C, 47.54 (47.58); H, 4.46 (4.54).

Example 6

Preparation of poly(dithiazolopyrrole-bisthienylethylene) (1d)

Dibromo-dithiazolopyrrole (2c) (36 mg, 0.065 mmol, 1 eq.) prepared as described in example 5, bis(2-trimethylstannyl-4-dodecylthienyl)ethylene (3d) (55.4 mg, 0.065 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (3.6 mg, 0.004 mmol, 6% eq.) and tri-o-tolylphosphine (2.4 mg, 0.008 mmol, 12% eq.) are added into a Schlenk flask and degassed 3 times. Chlorobenzene (1.5 mL) is added and the reaction mixture is stirred at 130° C. for 2 days. After two days of reaction, tris(dibenzylideneacetone)dipalladium(0) (3.6 mg, 0.004 mmol, 6% eq.) and tri-o-tolylphosphine (2.4 mg, 0.008 mmol, 12% eq.) was added. After total reaction of 3 days, the polymerization is stopped by the addition of 2-bromothiophene (0.01 mL) followed by 2-tributylstannylthiophene (0.01 mL) 3 hours later. After another 3 hours stirring, the reaction mixture is cooled to room temperature and added dropwise to methanol (100 mL), filtered, and then subjected to Soxhlet extraction with acetone. The polymer is recovered as solid mass and showed Mn=4305 g/mol (Mw=7571 g/mol & D=1.76).

Measurement of the Ionization Potential of Polymer 1a

The oxidative stability of π-conjugated polymers may be contributed by their ionization potential (IP), that is, on the energy of the highest occupied molecular orbital (HOMO) with respect to vacuum. The ionization potential (IP) is also reflected as negative value of the HOMO energy level (E_HOMO) of a molecule, oligomer or polymer,
IP=−E _HOMO
and can be measured by cyclic voltammetry (CV).
The HOMO energy levels (E_HOMO) of poly(benzobisthiazole-cyclopentadithiophene) (1a), prepared as described in example 2, and comparative polymer 22a, which is described by Xiao, S; Zhou H.; You, W. in Macromolecules 2008, 41, 5688-5696, are determined by cyclic voltammetry (CV).
Cyclic voltamogramms are recorded from thin films of polymer 1a, respectively comparative polymer 22a, drop-casted from 0.5 mg/mL chloroform solutions. A Pt disk is used as a working electrode and Ag/AgCl reference electrode is employed. The measurement is done in tetrabutylammonium tetrafluoroborate as electrolyte and ferrocene/ferrocenium redox couple (Fc/Fc⁺) is used as an internal reference, which has a known reduction potential of 4.8 eV. The electrochemical (oxidation and reduction) onset is determined at the position where the current starts to differ from the baseline and the HOMO energy level (E_HOMO) is calculated from the onset oxidation potential (E_Ox), as shown in the equation below:
E _HOMO=−(E _Ox+4.8)[eV]
The results are outlined in table 1.

	TABLE 1

	polymer	E_HOMO[eV]

	1a	−5.44
	22a (comparative)	−5.04

As can be derived from table 1, the HOMO energy level (E_HOMO) value of polymer 1a is decreased by 0.4 eV compared to the HOMO energy level (E_HOMO) value of comparative polymer 22a, and thus the ionization potential (IP) and consequently the oxidative stability of polymer 1a is higher than the one of comparative polymer 22a.
Fabrication of an Organic Field-Effect Transistor using Polymer 1a as Semiconductor
An organic field effect transistor is made in bottom gate bottom contact (BGBC) architecture, as depicted in FIG. 1. Heavily doped Si wafer are used as substrate and gate electrode with 200 nm thermally grown SiO₂serving as gate dielectric. Source and drain electrode are made of gold which is lithographically patterned. Before semiconductor deposition, the substrate is vapor treated with hexamethyldisilazane (HMDS). The polymer 1a solution is prepared by solubilizing the polymer 1a in 1,2-dichloro-benzene and heating it inside oven until soluble. Subsequently, semiconductor solution deposition of the polymer 1a is done by spin coating (deposition condition: 2000 rpm, 255 acc, 1 minute). The organic field effect transistor is made in ambient environment.
Testing of the Organic Field-Effect Transistor using Polymer 1a as Semiconductor
The hole mobility (μ_o), onset voltage (V_on, voltage when the drain current increases abruptly and can be measured), and the on/off ratio of the organic field effect transistor using polymer 1a as semiconductor are determined at room temperature and after annealing at 200° C. for 30 minutes, in order to observe the effect of annealing on the semiconductor performance. The organic field effect transistor is tested in ambient environment. Channel length (L)=5 μm, Channel width (W)=350 μm, W/L=70. Measurement is performed at: gate voltage (Vg)=sweep from 20 to −90 V, drain voltage (Vd)=−90 V,
The results are outlined in table 2.

TABLE 2

hole mobility
μ_p[cm²/Vs]	V_on[V]	On/Off ratio

at RT	0.2 × 10⁻³	−5	2.66 × 10⁴
after annealing	1.06 × 10⁻³	5	6.01 × 10⁴
at 200° C.

Claims

1. A compound of formula

wherein

A¹and A²are independently S or Se,

E is selected from the group consisting of

wherein

R¹and R²are independently 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, —X¹—R⁶, —X²—Ar¹, —X²—Ar²—Ar¹, —X²—Ar²—R⁷or —X²—Ar²—Ar³—R⁷,

wherein

X¹is —O—, —[Z¹—O]_a—, —[O—Z¹]_a—O—, —S—, —[Z¹—S—]_a—, —[S—Z¹]_a—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR⁸—, C(O)S—, —O(CO)—, —S(CO)—, —NR⁸C(O)— or —NR⁸—,

wherein

Z¹is C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,

a is an integer of from 1 to 10, and

R⁸is H, C_1-20-alkyl, or —Z²—C_6-14-aryl,

wherein

Z²is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

R⁶is C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,

X²is —Z³—O—Z⁴—, —Z³—S—Z⁴—, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR⁹, —C(O)S—, —O(CO)—, —S(CO)—, —NR⁹C(O)—, —NR⁹—, —Z³—SiR⁹ ₂—Z⁴—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein

Z³and Z⁴are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and

R⁹is H, C_1-20-alkyl, or —Z⁵—C_6-14-aryl,

wherein

Z⁵is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar¹is C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^a, wherein R^ais selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl,

Ar²and Ar³are 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 R^bis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R⁷is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X³—Ar⁴, —X³—Ar⁵—Ar⁴, —X³—Ar⁵—R¹⁰, or —X³—Ar⁵—Ar⁶—R¹⁰,

wherein

X³is —Z⁶—O—Z⁷—, —Z⁶—S—Z⁷, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR¹¹, —C(O)S—, —O(CO)—, —S(CO)—, —NR¹¹C(O)—, —NR¹¹—, —Z⁶—SiR¹¹ ₂—Z⁷—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein

Z⁶and Z⁷are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and

R¹¹is H, C_1-20-alkyl or —Z⁸—C_6-14-aryl,

wherein

Z⁸is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar⁴is C_6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R^c, wherein R^cis independently selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl,

Ar⁵and Ar⁶at 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 R^dis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R¹⁰is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,

R³, R⁴and R⁵are independently 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, —X⁴—R¹², —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,

wherein

X⁴is —[Z⁹—O]_b—, —[Z⁹—S—]_b—, —S(O)—, —C(O)—, —C(O)O—, —C(O)NR¹⁴— or C(O)S—,

wherein

Z⁹is C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,

b is an integer of from 1 to 10, and

R¹⁴is H, C_1-20-alkyl, or —Z¹⁰—C_6-14-aryl,

wherein

Z¹⁰is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

R¹²is C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,

X⁵is —Z¹¹—O—Z¹², —Z¹¹—S—Z¹²—, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR¹⁵, —C(O)S—, —Z¹¹—SiR¹⁵ ₂—Z¹²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein

Z¹¹is C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,

Z¹²is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and

R¹⁵is H, C_1-20-alkyl, or —Z¹³—C_6-14-aryl,

wherein

Z¹³is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar⁷is C_6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R^e, wherein R^eis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl,

Ar⁸and Ar⁹are 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 R^fis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R¹³is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁶—Ar¹⁰, —X⁶—Ar¹¹—Ar¹⁰, —X⁶—Ar¹¹—R¹⁶, or —X⁶—Ar¹¹—Ar¹²—R¹⁷,

wherein

X⁶is —Z¹⁴—O—Z¹⁵—, —Z¹⁴—S—Z¹⁵, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR¹⁸, —C(O)S—, —O(CO)—, —S(CO)—, —NR¹⁸C(O)—, —NR¹⁸—, —Z¹⁴—SiR¹⁸ ₂—Z¹⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein

Z¹⁴and Z¹⁵are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and

R¹⁸is H, C_1-20-alkyl or —Z¹⁶—C_6-14-aryl,

wherein

Z¹⁶is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar¹⁰is C_6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R^g, wherein R^gis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl,

Ar¹¹and Ar¹²are independently C_6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R^h, wherein R^his selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R¹⁷is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,

R¹⁹is O or C(CN)₂, and

R²⁰and R²¹are independently R²²or CN,

wherein R²²has the same meaning as R¹,

G¹and G²are independently phenylene or a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents Rⁱ, wherein Rⁱis selected from the group consisting of a halogen, a —CN, a —NO₂, a OH, a C_1-30-alkyl, a C_2-30-alkenyl, a C_2-30-alkynyl, a —Z¹⁷—O—C_1-30-alkyl, a —Z¹⁷—S—C_1-30-alkyl, a —Z¹⁷—C_3-10-cycloalkyl, a —Z¹⁷—C_5-10-cycloalkenyl, a —Z¹⁷—C_8-10-cycloalkynyl, a —Z¹⁷—C_6-14-aryl, a —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and a —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein

C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_5-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^j, wherein R^jis selected from the group consisting of a halogen, a —CN, a —NO₂, a *═O, a —OH, a —NH₂, a —NH(C_1-20-alkyl), a —N(C_1-20-alkyl)₂, a —N(C_1-20-alkyl)-C_6-14-aryl, a —N(C_6-14-aryl)₂, a —S(O)_mH, a —S(O)_m—C_1-20-alkyl, a —S(O)₂OH, a —S(O)_m—OC_1-20-alkyl, a —S(O)_m—OC_6-14-aryl, a —CHO, a —C(O)—C_1-20-alkyl, a —C(O)—C_6-14-aryl, a —C(O)OH, a —C(O)—OC_1-20-alkyl, a —C(O)—OC_6-14-aryl, a —C(O)NH₂, a —C(O)NH—C_1-20-alkyl, a —C(O)N(C_1-20-alkyl)₂, a —C(O)NH—C_6-14-aryl, a —C(O)N(C_1-20-alkyl)-C_6-14-aryl, a —C(O)N(C_6-14-aryl)₂, a —C(S)NH₂, —C(S)NH—C_1-20-alkyl, a —C(S)N(C_1-20-alkyl)₂, a —C(S)N(C_6-14-aryl)₂, a —C(S)N(C_1-20-alkyl)-C_6-14-aryl, a —C(S)NH—C_6-14-aryl, a —S(O)_mNH₂, a —S(O)_mNH(C_1-20-alkyl), a —S(O)_mN(C_1-20-alkyl)₂, a —S(O)_mNH(C_6-14-aryl), a —S(O)_mN(C_1-20-alkyl)-C_6-14-aryl, a —S(O)_mN(C_6-14-aryl)₂, a SiH₃, a SiH(C_1-20-alkyl)₂, a SiH₂(C_1-20-alkyl) and a Si(C_1-20-alkyl)₃,

wherein m is an integer of 0, 1 or 2,

wherein C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^k, wherein R^kis selected from the group consisting of a C_1-20-alkyl, a C_2-20-alkenyl, a C_2-20-alkynyl, a C_1-20-alkoxy, a —S—C_1-20-alkyl, and a C_1-20-haloalkyl, and

Z¹⁷is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

L is C_6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R^l, wherein R^lis selected from the group consisting of a halogen, a —CN, a —NO₂, a *═O, a OH, a *═C(C_1-30-alkyl)₂, a C_1-30-alkyl, a C_2-30-alkenyl, a C_2-30-alkynyl, a —Z¹⁸—O—C_1-30-alkyl, a —Z¹⁸—S—C_1-30-alkyl, a —Z¹⁸—C_3-10-cycloalkyl, a —Z¹⁸—C_5-10-cycloalkenyl, a —Z¹⁸—C_8-10-cycloalkynyl, a —Z¹⁸—C_6-14-aryl, a —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and a —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein

C_1-30-alkyl, C_2-30-alkenyl, C_2-30-alkynyl, C_3-10-cycloalkyl, C_5-10-cycloalkenyl, C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^m, wherein R^mis selected from the group consisting of a halogen, a —CN, a —NO₂, a *═O, a —OH, a —NH₂, a —NH(C_1-20-alkyl), a —N(C_1-20-alkyl)₂, a —N(C_1-20-alkyl)-C_6-14-aryl, a —N(C_6-14-aryl)₂, a —S(O)_mH, a —S(O)_o—C_1-20-alkyl, a —S(O)₂OH, a —S(O)_o—OC_1-20-alkyl, a —S(O)_o—OC_6-14-aryl, a —CHO, a —C(O)—C_1-20-alkyl, a —C(O)—C_6-14-aryl, a —C(O)OH, a —C(O)—OC_1-20-alkyl, a —C(O)—OC_6-14-aryl, a —C(O)NH₂, a —C(O)NH—C_1-20-alkyl, a —C(O)N(C_1-20-alkyl)₂, a —C(O)NH—C_6-14-aryl, a —C(O)N(C_1-20-alkyl)-C_6-14-aryl, a —C(O)N(C_6-14-aryl)₂, a —C(S)NH₂, a —C(S)NH—C_1-20-alkyl, a —C(S)N(C_1-20-alkyl)₂, a —C(S)N(C_6-14-aryl)₂, a —C(S)N(C_1-20-alkyl)-C_6-14-aryl, a —C(S)NH—C_6-14-aryl, a —S(O)_oNH₂, a —S(O)_oNH(C_1-20-alkyl), a —S(O)_oN(C_1-20-alkyl)₂, a —S(O)_oNH(C_6-14-aryl), a —S(O)_oN(C_1-20-alkyl)-C_6-14-aryl, a —S(O)_oN(C_6-14-aryl)₂, a SiH₃, a SiH(C_1-20-alkyl)₂, a SiH₂(C_1-20-alkyl) and a Si(C_1-20-alkyl)₃,

wherein o is an integer of 0, 1 or 2,

C_3-10-cycloalkyl, C_5-10-cycloalkenyl, —C_8-10-cycloalkynyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents Rⁿ, wherein Rⁿis selected from the group consisting of a C_1-20-alkyl, a C_2-20-alkenyl, a C_2-20-alkynyl, a C_1-20-alkoxy, a —S—C_1-20-alkyl, and a C_1-20-haloalkyl, and

Z¹⁸is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

or

L is

wherein

R²³and R²⁴are independently 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, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,

wherein

X⁷is —O—, —[Z¹⁹—O]_c—, —[O—Z¹⁹]_c—O—, —S—, —[Z¹⁹—S—]_c—, —[S—Z¹⁹]_c—S—, —S(O), —C(O)—, —C(O)O—, —C(O)NR²⁷—, C(O)S—, —O(CO)—, —S(CO)—, —NR²⁷C(O)— or —NR²⁷—,

wherein

Z¹⁹is C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene,

c is an integer of from 1 to 10, and

R²⁷is H, C_1-20-alkyl, or —Z²⁰—C_6-14-aryl,

wherein

Z²⁰is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

R²⁵is C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,

X⁸is —Z²¹—O—Z²², —Z²¹—S—Z²²—, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR²⁸, —C(O)S—, —O(CO)—, —S(CO)—, —NR²⁸C(O)—, —NR²⁸—, —Z²¹—SiR²⁸ ₂—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein

Z²¹and Z²²are C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and

R²⁸is H, C_1-20-alkyl, or —Z²³—C_6-14-aryl,

wherein

Z²³at each occurrence is independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar¹³is C_6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R^o, wherein R^ois selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl,

Ar¹⁴and Ar¹⁵are C_6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R^p, wherein R^pis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R²⁶is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl, C_1-20-alkoxy, —X⁹—Ar¹⁶, —X⁹—Ar¹⁷—Ar¹⁶, —X⁹—Ar¹⁷—R²⁹, or X⁹—Ar¹⁷—Ar¹⁸—R²⁹,

wherein

X⁹is —Z²⁴—O—Z²⁵—, —Z²⁴—S—Z²⁵, —S(O)—, —C(O)—, —C(O)O—, —(CO)NR³⁰, —C(O)S—, —O(CO)—, —S(CO)—, —NR³⁰C(O)—, —NR³⁰—, —Z²⁴—SiR³⁰ ₂—Z²⁵—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein

Z²⁴and Z²⁵are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond, and

R³⁰is H, C_1-20-alkyl or —Z²⁶—C_6-14-aryl,

wherein

Z²⁶is C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar¹⁶is C_6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R^q, wherein R^qis selected from the group consisting of a halogen, CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl,

Ar¹⁷and Ar¹⁸are independently C_6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R^r, wherein R^ris selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R²⁹is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy,

q and s are independently an integer of 0, 1, 2, 3, 4 or 5,

r is an integer of 0, 1 or 2, and

n is an integer of from 1 to 10,000.

2. The compound of claim 1, wherein A¹and A²are S.

3. The compound of claim 1, wherein E is selected from the group consisting of

4. The compound of claim 1, wherein E is

5. The compound of claim 1, wherein E is

6. The compound of claim 1, wherein R¹and R²are independently H, C_1-30-alkyl, C_1-30-haloalkyl, —X¹—R⁶or —X²—Ar¹,

wherein

X¹is —[Z¹—O]_a—, —[Z¹—S—]_a—, or —[S—Z¹]_a—S—,

wherein

Z¹is C_1-6-alkylene or C_1-6-haloalkylene, and

a is an integer of from 1 to 10,

R⁶is C_1-30-alkyl or C_1-30-haloalkyl,

X²is —Z³—O—Z⁴—, —Z³—S—Z⁴—, C_1-30-alkylene or C_1-30-haloalkylene,

wherein Z³and Z⁴are independently C_1-6-alkylene or C_1-6-haloalkylene,

and

Ar¹is C_6-14-aryl, optionally substituted with 1 to 5 substituents R^a, wherein R^ais selected from the group consisting of a halogen, a C_1-6-alkyl, and a C_1-6-alkoxy.

7. The compound of claim 1, wherein R¹and R²are independently a C_1-30-alkyl.

8. The compound of claim 1, wherein R³is —X⁵—Ar⁷, —X⁵—Ar⁸—Ar⁷, —X⁵—Ar⁸—R¹³or —X⁵—Ar⁸—Ar⁹—R¹³,

wherein

X⁵is a covalent bond,

R¹³is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

9. The compound of claim 1, wherein R³is —X⁵—Ar⁸—R¹³,

wherein

X⁵is a covalent bond,

Ar⁸is C_6-14-arylene, and

R¹³is C_1-20-alkyl.

10. The compound of claim 1, wherein G¹and G²are independently a phenylene

or, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of

wherein phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents Rⁱ, wherein Rⁱis selected from the group consisting of a C_1-30-alkyl, a —Z¹⁷—O—C_1-30-alkyl, a —Z¹⁷—S—C_1-30-alkyl, a —Z¹⁷—C_3-10-cycloalkyl, a —Z¹⁷—C_6-14-aryl, a —Z¹⁷-monovalent 3 to 12 membered aliphatic heterocyclic residue and a —Z¹⁷-monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein

C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents wherein is independently selected from the group consisting of a halogen, a —CN and a *═O,

C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R^k, wherein R^kis independently selected from the group consisting of a C_1-20-alkyl, a C_1-20-alkoxy, and a C_1-20-haloalkyl,

and

Z¹⁷is C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond.

11. The compound of claim 1, wherein G¹and G²are independently a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue

which is substituted with 1 to 2 substituents Rⁱ, wherein Rⁱis selected from the group consisting of a C_1-30-alkyl and a —Z¹⁷—C_6-14-aryl,

wherein

C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^j, wherein R^jis selected from the group consisting of a halogen, a —CN and a *═O,

C_6-14-aryl is optionally substituted with 1 to 4 substituents R^k, wherein R^kis selected from the group consisting of a C_1-20-alkyl and a C_1-20-alkoxy, and

Z¹⁷is a covalent bond.

12. The compound of claim 1, wherein Rⁱis C_1-30-alkyl.

13. The compound of claim 1, wherein

L is a bivalent 5 to 18 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents R^l, wherein R^lis selected from the group consisting of a C_1-30-alkyl, a —Z¹⁸—O—C_1-30-alkyl, a —Z¹⁸—S—C_1-30-alkyl, a —Z¹⁸—C_3-10-cycloalkyl, a —Z¹⁸—C_6-14-aryl, a —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and a —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein

C_1-30-alkyl, C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R^m, wherein R^mis selected from the group consisting of a halogen, a —CN and a *═O,

C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein Rⁿis selected from the group consisting of a C_1-20-alkyl, a C_1-20-alkoxy, and a C_1-20-haloalkyl,

and

Z¹⁸is C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,

or

L is

wherein R²³and R²⁴are independently H, halogen, —CN, C_1-30-alkyl, C_2-30-alkenyl, C_1-30-haloalkyl, —X⁷—R²⁵, —X⁸—Ar¹³, —X⁸—Ar¹⁴—Ar¹³, —X⁸—Ar¹⁴—R²⁶or —X⁸—Ar¹⁴—Ar¹⁵—R²⁶,

wherein

X⁷is —O—, —[Z¹⁹—O]_c—, —[O—Z¹⁹]_c—O—, —S—, —[Z¹⁹—S]_c— or —[S—Z¹⁹]_c—S—,

wherein

Z¹⁹is C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene, and

c is an integer of from 1 to 10,

R²⁵is C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,

X⁸is Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene, C_2-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein Z²¹and Z²²re independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

Ar¹⁴and Ar¹⁵are independently C_6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R^p, wherein R^pis selected from the group consisting of a halogen, a CN, a C_1-6-alkyl, a C_1-6-alkoxy and a C_1-6-haloalkyl, and

R²⁶is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

14. The compound of claim 1, wherein

L is a bivalent 5 to 18 membered aromatic heterocyclic residue selected from the group consisting of

wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents

wherein R^lis selected from the group consisting of a C_1-30-alkyl, a —Z¹⁸—O—C_1-30-alkyl, a —Z¹⁸—S—C_1-30-alkyl, a —Z¹⁸—C_3-10-cycloalkyl, a —Z¹⁸—C_6-14-aryl, a —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and a —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein

C_3-10-cycloalkyl, C_6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents Rⁿ, wherein Rⁿis selected from the group consisting of a C_1-20-alkyl, a C_1-20-alkoxy, and a C_1-20-haloalkyl, and

Z¹⁸is C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,

and

R^tis hydrogen or C_1-30-alkyl,

or

L is

wherein

X⁷is —O—, —[Z¹⁹—O]_c—, —[O—Z¹⁹]_c—O—, —S—, —[Z¹⁹—S—]_c— or —[S—Z¹⁹]_c—S—,

wherein

Z¹⁹is C_1-6-alkylene, C_1-6-alkenylene or C_1-6-haloalkylene, and

c is an integer of from 1 to 10,

R²⁵is C_1-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl,

X⁸is —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene, C_1-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein Z²¹and Z²²are independently C_1-6-alkylene, C_1-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

R²⁶is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

15. The compound of claim 1, wherein

L is

wherein R¹is selected from the group consisting of a C_1-30-alkyl, a —Z¹⁸—O—C_1-30-alkyl, a —Z¹⁸—S—C_1-30-alkyl, a —Z¹⁸—C_3-10-cycloalkyl, a —Z¹⁸—C_6-14-aryl, a —Z¹⁸-monovalent 3 to 12 membered aliphatic heterocyclic residue and a —Z¹⁸-monovalent 5 to 14 membered aromatic heterocyclic residue.

wherein

Z¹⁸is C_1-6-alkylene, C_1-6-haloalkylene or a covalent bond,

or

L is

wherein

Z¹⁹is C_1-6-alkylene, C_2-6-alkenylene or C_1-6-haloalkylene, and

c is an integer of from 1 to 10,

R²⁵is C_3-30-alkyl, C_2-30-alkenyl or C_1-30-haloalkyl.

X⁸is Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene, C_1-30-alkenylene, C_1-30-haloalkylene or a covalent bond,

wherein Z²¹and Z²²are independently C_1-6-alkylene, C_2-6-alkenylene, C_1-6-haloalkylene or a covalent bond,

R²⁶is C_1-20-alkyl, C_2-20-alkenyl, C_1-20-haloalkyl or C_1-20-alkoxy.

16. The compound of claim 1, wherein

R^lis selected from the group consisting of a C_1-30-alkyl and a —Z¹⁸—C_6-14-aryl,

wherein

C_1-30-alkyl and C_6-14-aryl are optionally substituted with 1 to 4 substituents R^m, wherein R^mis selected from the group consisting of a halogen, a —CN and a *═O,

C_6-14-aryl is optionally substituted with 1 to 4 substituents Rⁿ, wherein Rⁿis selected from the group consisting of a C_1-20-alkyl and a C_1-20-alkoxy, and

Z¹⁸is a covalent bond,

and

R²³and R²⁴are independently H, C_1-30-alkyl, C_1-30-haloalkyl, —X⁷—R²⁵or —X⁸—Ar¹³,

wherein

X⁷is —[Z¹⁹—O]_c—, —[Z¹⁹—S—]_c—, or —[S—Z¹⁹]_c—S—,

wherein

Z¹⁹is C_1-6-alkylene or C_1-6-haloalkylene, and

c is an integer of from 1 to 10,

R²⁵is C_1-30-alkyl or C_1-30-haloalkyl,

X⁸is —Z²¹—O—Z²²—, —Z²¹—S—Z²²—, C_1-30-alkylene or C_1-30-haloalkylene,

wherein Z²¹and Z²²are independently C_1-6-alkylene or C_1-6-haloalkylene,

and

Ar¹³is C_6-14-aryl, optionally substituted with 1 to 5 substituents R^o, wherein R^ois selected from the group consisting of a halogen C_1-6-alkyl and a C_1-6-alkoxy.

17. The compound of claim 1, wherein R^lis C_1-30-alkyl,

and

R²³and R²⁴are independently H, C_1-30-alkyl or C_1-30-haloalkyl.

18. The compound of claim 1, wherein q, r and s are an integer of 0 or 1, and q, r and s are not all 0 at the same time.

19. The compound of claim 1, wherein n is an integer of from 1 to 5000.

20. An electronic device comprising the compound of claim 1.

21. The electronic device of claim 20, wherein the electronic device is an organic field effect transistor.

22. An organic semiconducting material comprising the compound of claim 1.