WO2015015397A1

WO2015015397A1 - Substituted naphthyridines as acceptor molecules for electronic devices

Info

Publication number: WO2015015397A1
Application number: PCT/IB2014/063478
Authority: WO
Inventors: Claudia TEUSCH; Manuel HAMBURGER; Klaus MÜLLEN; Stefan HÖFLE; Alexander Colsmann; Uli Lemmer
Original assignee: BASF China Co Ltd; INNOVATION LAB GmbH; Lichttechnisches Institut LTI KIT; Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Current assignee: BASF China Co Ltd; INNOVATION LAB GmbH; Lichttechnisches Institut LTI KIT; Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Priority date: 2013-07-30
Filing date: 2014-07-28
Publication date: 2015-02-05
Anticipated expiration: 2016-01-30
Also published as: TW201522335A

Abstract

The present invention provides the compounds of formula (1) wherein p is 1, 2, 3, 4, 5 or 6, and10 Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of C_1-20-alkyl, O-C_1-20-alkyl, C(O)-C_1-20-alkyl, C(O)-O-C_1-20-alkyl, phenyl, F, Cl and Br, wherein C_1-20-alkyl, C_1-20-alkyl, O-C_1-20-alkyl, C(O)-C_1-20-alkyl and C(O)-O-C_1-20-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, Cl, Br and phenyl, wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, Cl, Br and C_1-10-alkyl, and electronic devices comprising these compounds.

Description

Substituted Naphthyridines as Acceptor Molecules for Electronic Devices

Description The present invention relates to substituted naphthyridines, to a process for the preparation of these substituted naphthyridines, to electronic devices comprising these substituted naphthyridines and to the use of these substituted naphthyridines as semiconducting materials.

Substituted naphyridines are suitable as semiconducting materials for use in electronic devices such as organic photovoltaic (OPV) cells, organic field-effect transistors (OFET) and organic light emitting diodes (OLED).

WO 2006/098121 describes compounds of general formula An-L-Ar₂, wherein An and Ar₂, respectively, represent a hydrogen atom or a substituent, and at least one of An and Ar₂ is an aromatic hydrocarbon fused ring or an aromatic heterocyclic fused ring wherein aromatic hydrocarbon rings or aromatic heterocyclic rings are fused, and L represents a linked group connected by a conjugated system containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Among the listed compounds is the following compound

US 2006/0113527 describes star-shaped compounds of formula

wherein p is an integer between 3 and 8, n and o are independently an integer between 0 and 6, and m is an integer between 2 and 8. Among the listed compounds for Ar is

The compounds are used as semiconductors in field effect transistors. US 2007/0166871 describes compounds of formula (Ai)-(X)_n-(A₂), wherein X is independently selected from the group consisting of unsubstituted and substituted C6-C3o-aryl groups and a substituted and unsubstituted C2-C2o-heteroaryl groups containing sulfur (S) or selenium (Se), Ai and A₂ are each independently selected from a C₂-C₂o-heteroaryl group containing nitrogen (N) or oxygen (O) and wherein n is 2 to 10. Among the listed examples for X is

Among the listed examples for Ai and A₂ is

The compounds are used as semiconducting materials in electronic devices.

US 2008/0116789 describes the following compounds

R

Among the exemplified compounds is

WO 2012/1 1181 1 describes the following p-type semiconductor materials

Among the listed examples for A is

Among the listed examples for the compounds is

JP 2004-327106 describes compounds of formula

wherein R¹ is aryl, and A and B are hydrogen or of formula

wherein A is a five or six-membered ring. It was the object of the present invention to provide new substituted naphthyridine derivatives.

This object is solved by the compounds of claim 1 , the process of claim 14 and the electronic device of claim 15.

The compounds of the present invention are of formula

(1 ) wherein

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6 L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H, Ci-20-alkyl, C(0)-Ci-2o-alkyl, Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl,

Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci-₂₀-alkyl, C(0)-Ci_-2o-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br, wherein Ci-₂₀-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_₁₀-alkyl, and

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci-₂o-alkyl, phenyl, F, CI and Br,

wherein Ci-₂₀-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(0)-Ci-₂o-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i₀-alkyl.

Ci-io-alkyl and Ci-20-alkyl can be branched or unbranched. Examples of Ci-10-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl. Examples of Ci-2o-alkyl are Ci-10-alkyl and n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂o).

Examples of 5 to 9-membered heteroaromatic moieties are

g

wherein R¹⁰⁰ is at each occurrence Ci-₁₀-alkyl or phenyl.

Examples of 5 to 14 membered heteroaromatic moieties are the examples given for the 5 to 9 membered heteroaromatic moieties and

Preferred compounds of formula (1 ) are of formula

wherein

p, n, q, L¹, Ar¹ and Ar² are as defined for the compound of formula (1 ).

Preferably, the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A5) ' (A6)

(B1 ) (B2) (B3) (B4)

(B9) (B10) wherein

X is O, S, Se or N-R¹⁰⁰,

wherein R¹⁰⁰ is d-10-alkyl or phenyl, and

Y is at each occurrence CH or N .

More preferably, the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 ) (A2a) (A3a) (A4a)

(A5a) (A6a)

(B1 ) (B2) (B3a) (B4a)

(B9a) (B10a) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-10-alkyl or phenyl, and

Y is at each occurrence CH or N .

Even more preferably, the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 ) (B1 ) (B2) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci 10-alkyl or phenyl, and

Y is at each occurrence CH or N .

Most preferably, the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 a) wherein

Y is at each occurrence CH or N .

particular, the 5 to 9 membered heteroaromatic moiety ^'

(A1b) (B1 b)

Preferably, Ar² is a C6-i4-aromatic moiety, wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(0)-0-Ci-₂o-alkyl, phenyl, F, CI and Br,

wherein Ci_-2o-alkyl, Ci_-2o-alkyl, 0-Ci_-2o-alkyl, C(0)-Ci_-2o-alkyl and C(0)-0-Ci_-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl. More preferably, Ar² is a C6-i4-aromatic moiety selected from the group consisting of

wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(O)- Ci-20-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

Preferably, p is 1 , 2 or 3. More preferably, p is 1 or 2. Preferably, n is 0 or 1 . More preferably, n is 0.

Preferably, q is 0, 1 , 2 or 3. More preferably, q is 0 or 1. Most preferably, q is 0.

Preferably, L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H , Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl.

More preferably, L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H or Ci-₂o-alkyl. Most preferably, L¹ is

wherein R⁵⁰ and R⁵¹ are H .

In preferred compounds of formula (1 )

p is 1 , 2, 3, 4, 5 or 6,

n is 0, 1 or 2,

q is O, 1 , 2, 3, 4, 5 or 6,

L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H, Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl,

Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 ) - (A2) , (A3) , (A4)

(A5) ' (A6)

(B9) (B10) wherein

X is O, S, Se or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-₁₀-alkyl or phenyl, and

Y is at each occurrence CH or N, which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-C1-20- alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i₀-alkyl, and

In more preferred compounds of formula (1 )

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6, L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H or Ci-20-alkyl,

(A1 ) (A2a) (A3a) (A4a)

N

(A5a) (A6a)

(B5a) (B6a) (B7a) (B8a)

(B9a) (B10a) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-10-alkyl or phenyl, and

Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-C1-20- alkyl, C(O)-Ci-₂₀-alkyl, C(0)-0-Ci_-2o-alkyl, phenyl, F, CI and Br,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and C-i-io-alkyl, and

In even more preferred compounds of formula (1 ) the compounds of formula (1 ) are of formula

wherein

p is 1 , 2 or 3,

n is 0 or 1 ,

q is 0, 1 , or 3

L¹ is

wherein R⁵⁰ and R⁵¹ are H,

(A1 ) (B1 ) (B2) wherein X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-i₀-alkyl or phenyl, and

Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-Ci-₂₀- alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci_-2o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, O-Ci-20-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and

Ar² is at each occurrence a C6-i4-aromatic moiety, wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br,

wherein Ci-₂₀-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl.

In most preferred compounds of formula (1 ) the compounds of formula (1 ) are of formula

wherein

p is 1 or 2,

n is 0,

q is 0 or 1 , Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 bered heteroaromatic moiety is selected from the group consisting of

(A1 a) (B1a) wherein

Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substitu- ents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-C1-20- alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci_₂o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

Ar² is at each occurrence a C6-i4-aromatic moiety selected from the group consisting of

wherein the C6-i4-aromatic moiety may be substituted with one or more substituents inde- pendently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(O)- Ci-20-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, Ci-₂o-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci_2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl. In particular preferred compounds of formula (1 ) the compounds of formula (1 ) are of formula

wherein

p is 1 or 2,

n is 0,

q is 0, and

(A1 b) (B1 b) which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substitu- ents independently from each other selected from the group consisting of Ci-20-alkyl and C(O)- Ci-2o-alkyl,

wherein Ci-₂o-alkyl and C(0)-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F and phenyl.

Also part of the present invention is a process for preparation of the compounds of formula

(1 ) wherein

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2, q is 0, 1 , 2, 3, 4, 5 or 6

L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H, Ci-2o-alkyl, C(0)-Ci_2o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl,

Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-₁₀-alkyl, and

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6 i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, 0-Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci-₂o-alkyl, phenyl, F, CI and Br,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-₁₀-alkyl, which process comprises the step of treating a compound of formula

(3) wherein Z^; is CI, Br, I or OSO2CF3, with a compound of formula

(2) wherein p, n, q, L¹, Ar¹ and Ar² are as defined for the compound of formula (1 ) and R⁷⁰ is

Ci-io-alkyl, in the presence of catalyst I.

Preferably, catalyst I is a palladium catalyst, for example bis(triphenylphosphine)palladium(ll)- chloride.

Preferably, the reaction is performed in a suitable solvent such as tetrahydrofuran. Preferably, the reaction is performed at elevated temperatures such as at a temperature in the range of 30 to 100 °C.

(1 ) wherein

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is O, 1 , 2, 3, 4, 5 or 6 selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H, Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(O)- Ci-2o-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl, Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group con- sisting of Ci_-2o-alkyl, O-Ci-₂₀-alkyl, C(0)-Ci_-2o-alkyl, C(0)-0-Ci_-2o-alkyl, phenyl, F, CI and Br, wherein Ci-₂₀-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, 0-Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,

wherein Ci-₂o-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_₁₀-alkyl, which process comprises the step of treating a compound of formula

wherein

Z¹ is CI, Br, I or OS0₂CF₃ with a compound of formula

(7')

wherein p, n, q, L¹, Ar¹ and Ar² are as defined for the compound of formula (1 ), and

Z² is CI, Br, I or OS0₂CF₃, in the presence of catalyst 11.

Catalyst II is preferably a nickel or palladium catalyst, for example Ni(dppp)Cl₂. The reaction is usually performed in a suitable solvent solvent, for example diethylether. The reaction is usually performed at slightly elevated temperatures such as in the range of 30 to 40 °C.

The compound of formula (7')

(7') wherein

p, n, q, L¹, Ar¹ and Ar² are as defined for the compound of formula (1 ), and

Z² is CI, Br, I or OSO2CF3, can be prepared by treating a compound of formula

(7) wherein

Z² is CI, Br, I or OS0₂CF₃, with magnesium.

The reaction is usually performed in a suitable solvent solvent, for example diethylether. The reaction is usually performed at slightly elevated temperatures such as in the range of 30 to 40 °C. The compound of formula

(7) can be prepared by treating a compound of formula

(8) with a Z²-donor-agent.

The reaction is usually performed in a suitable solvent such as dimethylformamide. When Z² is Br, the Z²-donor-agent can be N-bromosuccinimide. The compound of formula (3), wherein Z¹ is CI, can be prepared by treating a compound of formula

I _

O

(4) with phosphoroxy chloride.

The compound of formula (4) can be prepared by treating a compound of formula

(5) with methyltrioxorhenium and H2O2. Also part of the invention are polymers comprising a unit of formula

wherein

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6

L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H , Ci-2o-alkyl, C(0)-Ci_2o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl,

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, 0-Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci-₂o-alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyi and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

Preferably, the polymers of the present invention comprise at least 60% by weight of units of formula (10) based on the weight of the polymer.

More preferably, the polymers of the present invention comprise at least 80% by weight of units of formula (10) based on the weight of the polymer.

Most preferably, the polymers of the present invention essentially consist of units of formula (10).

In preferred polymers of the present invention comprising a unit of formula (10),

p is 1 , 2, 3, 4, 5 or 6,

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6,

L¹ is selected from the group consisting of

(A1) - (A2) , (A3) , (Α4)

(Α5) ' (Α6)

(Β1) (Β2) (Β3) (Β4)

(Β9) (Β10) wherein

XisO, S, Se or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-10-alkyl or phenyl, and

Y is at each occurrence CH or N, which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-C1-20- alkyl, C(0)-Ci-2o-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br,

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a Ce-M-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂₀-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci-₂o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl. In more preferred polymers of the present invention comprising a unit of formula (10) p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6, L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H or Ci-20-alkyl,

(A1) (A2a) (A4a)

(A5a) (A6a)

(B1) (B2) (B3a) (B4a)

N

(B9a) (B10a) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-10-alkyl or phenyl, and Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-C1-20- alkyl, C(0)-Ci-₂o-alkyl , C(0)-0-Ci_-2o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl ,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl.

I n even more preferred polymers of the present invention comprising a unit of formula (10) the unit of formula (10) is of formula

wherein

p is 1 , 2 or 3,

n is 0 or 1 ,

q is 0, 1 , or 3

L¹ is

wherein R⁵⁰ and R⁵¹ are H ,

Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9

bered heteroaromatic moiety is selected from the group consisting of

(A1 ) (B1 ) (B2) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-10-alkyl or phenyl, and

Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-Ci-₂₀- alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein Ci_₂o-alkyl, Ci-₂o-alkyl, 0-Ci_₂o-alkyl, C(0)-Ci_₂o-alkyl and C(0)-0-Ci_₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI , Br and phenyl, wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl.

In most preferred polymers comprising a unit of formula (10) the unit of formula (10) is of formula

wherein

p is 1 or 2,

n is 0,

q is 0 or 1 , Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 a) (B1a) wherein

Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, O-Ci-₂₀- alkyl, C(O)-Ci-₂₀-alkyl, C(0)-0-Ci_-2o-alkyl, phenyl, F, CI and Br,

wherein Ci-20-alkyl, O-Ci-20-alkyl, C(O)-Ci-₂₀-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(O)- Ci-20-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br,

wherein Ci-₂o-alkyl, Ci-₂o-alkyl, 0-Ci-₂o-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_₁₀-alkyl.

In particular preferred polymers comprising a unit of formula (10) the unit of formula (10) is of formula

wherein

p is 1 or 2,

n is 0,

q is 0, and Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 b) (B1 b) which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂₀-alkyl and C(O)- Ci-2o-alkyl, wherein Ci-20-alkyl and C(0)-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F and phenyl.

Also part of the present invention is a process for the preparation of the polymers comprising unit of formula

wherein

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6

L¹ is selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H, Ci-20-alkyl, C(0)-Ci-2o-alkyl, Ci-2o-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl,

Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br, wherein Ci-₂o-alkyl, Ci-₂o-alkyl, 0-Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyi and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, which process comprises the step of treating a compound of formula

wherein

p, n, q, L¹, Ar¹ and Ar² are as defined for the polymer comprising a unit of formula (10), and Z³ is CI, Br or I, with catalyst III.

Preferably, the catalyst III is a nickel catalyst. More preferably, it is an organonickel catalyst such as bis(1 ,5-cyclooctadiene)nickel(0). Preferably, a chelating ligand such as 2,2'-bipyridine is also present. Usually the reaction is performed in a suitable solvent, for example in dimethyl- formanide (DMF) or tetrahydrofuran or mixtures thereof. Usually the reaction is performed under inert atmosphere. Preferably, the reaction is performed at elevated temperatures, such as in the range of 40 to 100 °C, preferably 50 to 80 °C. The reaction can be terminated by addition of an endcapper, for example bromobenzene.

The compound of formula

wherein

p, n, q, L¹, Ar¹ and Ar² are as defined for the polymer comprising a unit of formula (10), and Z³ is CI, Br or I, can be prepared by treating a compound of formula

(1 ) wherein

p, n, q, L¹, Ar¹ and Ar² are as defined for the polymer comprising a unit of formula (10) with a Z³-donor-agent.

The reaction is usually performed in a suitable solvent such as dimethylformamide or dichloro- methane. When Z³ is Br, a suitable Z²-donor.agent is for example N-bromosuccinimide.

Also part of the present invention are compounds of formula

(9)

wherein

p is 1 , 2, 3, 4, 5 or 6

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6 L¹ is selected from the group consisting of

Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group con- sisting of Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br, wherein Ci-₂₀-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl, wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-₁0-alkyl, and

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i₄-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i₄-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂o-alkyl, 0-Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(0)-0-Ci-₂o-alkyl, phenyl, F, CI and Br,

wherein Ci-₂₀-alkyl, Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl and C(O)-O-Ci-₂₀-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl ,

Z³ is CI, Br or I .

Also part of the invention is an electronic device comprising the compounds or the 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). Prefera- bly, the electronic device is an organic light emitting diode.

Usually an organic light emitting diode comprises a substrate, an emission layer comprising an emitting material and a semiconducting material , an anode and a cathode. The organic light emitting diode can comprise additional layers such as enhanced hole injection layers, electron blocking layers and hole blocking layer.

An organic light emitting device can have various designs such as a bottom emission design or a top emission design. The substrate of the organic light emitting diode can be glass.

The emission layer comprises an emitting material and the compounds or polymers of the present invention. The compounds or polymers of the present invention function as semiconducting material. Examples of emitting materials are fluorescent dyes and phosphorescent dyes. Exam- pies of fluorescent dyes are perylene, rubrene and quinacridone-type dyes as well as Aluminium tris (8-hydroxychinolin) (Alq3) and tris(2-phenylpyridinato-C2,N)iridium(l l l) (l r(ppy)3).

The anode is typically indium tin oxide (ITO). The cathode can be LiF/AI. An example of an enhanced hole injection layer is a M0O3 layer. An examples of an electron blocking layer is tris (4-carbazol-9-yl-phenyl)amine (TCTA). An example of a hole blocking layer is 1 ,3,5,-tris(N-phenyl-2-bezimidazolyl)benzene (TPBi).

The layers are usually 2 to 100 nm thick, preferably 5 to 50 nm. The layers are usually applied by thermal evaporation. A typical organic light emitting diode is depicted in Figure 1.

Usually, an organic field effect transistor comprises a dielectric layer, a semiconducting layer and a substrate. In addition, an organic field effect transistor usually comprises a gate electrode and source/drain electrodes.

An organic field effect transistor can have various designs, for example bottom-gate design or top-gate design. The substrate of the organic field effect transistor can be any suitable substrate such as un- doped or highly doped silicon, for example in form of a silicon waver, or glass, or a plastic substrate such as polyethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). The dielectric layer comprises a dielectric material. The dielectric material can be any suitable material such as aluminium oxide, aluminium oxide in combination with a self-assembled monolayer (SAM) of a phosphonic acid such as Ci₄H₂9PO(OH)2 [TDPA] or C₇Fi5Cii H22PO(OH)2 [FODPA]), silicon dioxide, or an organic polymer such as polystyrene (PS), polymethylmethacrylate) (PM MA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), benzocyclobutene (BCB) or polyimide (PI), or a combination of these materials The dielectric layer can have a thickness of 5 to 2000 nm, preferably of 5 to 500 nm, more preferably of 5 to 100 nm.

The semiconducting layer of the organic field effect transistor comprises one or more of the compounds of the present invention. The semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.

The source/drain electrodes can be made from any suitable source/drain material, for example silver (Ag), gold (Au) or tantalum (Ta). The source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 5 to 50 nm.

The gate electrode can be made from any suitable gate material such as highly doped silicon, aluminium (Al), tungsten (W), indium tin oxide, silver (Ag), gold (Au) or tantalum (Ta), or from a combination of these materials. The gate electrode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.

The organic field effect transistor can be prepared by methods known in the art.

For example, a bottom-gate organic field effect transistor can be prepared as follows:

Aluminium can be deposited on highly doped silicon wafers by thermal evaporation, followed by oxidation of the aluminium layer to aluminium oxide and treatment of the aluminium oxide surface with a phosphonic acid in order to form a self-assembled monolayer (SAM-layer) of the phosphonic acid on the aluminium oxide surface. The semiconducting material can be deposited on the SAM-layer by thermal sublimation. The source and drain electrodes can be formed by evaporating gold through a shadow mask. The back side of the highly doped silicon wafers can be coated with silver ink to serve as the gate electrode. For example, a bottom-gate organic field effect transistor can be prepared as follows:

Aluminiumoxide can be deposited on highly doped silicon wafers with a thermally grown silicon dioxide layer by atomic layer deposition, followed by treatment of the aluminium oxide surface with a phosphonic acid in order to form a self-assembled monolayer (SAM-layer) of the phosphonic acid on the aluminium oxide surface. The semiconducting material can be deposited on the SAM-layer by thermal sublimation. The source and drain electrodes can be formed by evaporating gold through a shadow mask. The back side of the highly doped silicon wafers can be coated with silver ink to serve as the gate electrode.

Also part of the invention is the use of the compounds or polymers of the present invention as semiconducting materials.

The compounds and polymers of the present invention are suitable as semiconducting materials for use in electronic devices such as organic photovoltaic (OPV) cells, organic field-effect transistors (OFET) and organic light emitting diodes (OLED).The compounds and polymers of the present invention are in particular suitable as semiconducting materials for use in organic light emitting diodes (OLED). The compounds and polymers of the present invention are in particular suitable as semiconducting materials in combination with emitting materials such as fluorescent dyes and phosphorescent dyes, in particular phosphorescent dyes, in the emitting layer of an organic light emitting diode (OLED). The compounds and polymers of the present invention show improved charge carrier transport properties, improved light-emitting properties, and are stable with elapse of time. Examples

Preparation of compound 4

A mixture of 1 ,5-naphthyridine (5) (1.00 g, 7.68 mmol) and methyltrioxorhenium (MTO) (20.0 mg, 80.2 pmol) in CH2CI2 (6 mL) was treated with 2.8 mL of 35% aqueous H2O2

(31.7 mmol) and stirred for -30 h at room temperature. Then another portion of MTO (20.0 mg, 80.2 pmol) and 2.8 mL H₂0₂ were added and the suspension was stirred for an additional 40 h. The biphasic reaction mixture was then treated with a catalytic amount of MnC>₂ (5 mg) and stirred until oxygen evolution ceased (-1 h). Compound 4 was filtered off and washed with wa- ter and a small amount of acetone and dried in vacuo. Yield: 965 mg (5.95 mmol, 77 %).

H NMR (300.13 MHz, (CD₃)₂SO) δ (ppm) = 8.72 (d, J = 6.2 Hz, 2 H , H1 ), 8.29 (d, J = 9.0 Hz, 2 H , H3), 7.69 (dd, J = 8.9 Hz, J = 6.1 Hz, 2 H, H2). ³C{ H} NMR (75.48 MHz, (CD₃)₂SO) δ (ppm) = 137.43 (C1 ), 124.87 {CI), 1 16.09 (C3). Preparation of compound 3a

Compound 4 (500 mg, 3.08 mmol) was added to cold (0 °C), freshly distilled phosphoroxy chloride (20 mL), and the mixture was refluxed for 30 min. After cooling, the solution was carefully poured onto ice and neutralized with aqueous ammonia. The mixture was extracted with di- chloromethane. The combined organic layers were dried over anhydrous MgSC and the sol- vent was evaporated under reduced pressure. Column chromatography (silica gel, DCM) provided compound 3a as a colorless solid (91 .0 mg, 457 μιτιοΙ, 15 %). ¹H NMR (300.13 MHz, CDC ) δ (ppm) = 8.26 (d, J = 8.5 Hz, 2 H , H3), 7.64 (d, J = 8.7 Hz, 2 H, H2).¹³C{¹H} NMR (75.48 MHz, CDCI3) δ (ppm) = 151.78 (C1 ), 142.64 (C4), 139.29 (C3), 127.03 (C2). Example 2

Preparation of compound 1 a

(3a) (2a) (1 a)

A flame dried Schlenk flask was charged with compound 3a (50.0 mg, 251 μιηοΙ), bis(triphenyl- phosphine)palladium(l l) dichloride (35.2 mg, 50.2 μηιοΙ), 2-(tributylstannyl)thiophene (258 mg, 692 μιηοΙ), lithium chloride (63.8 mg, 1 .51 mmol) and dry TH F (2 ml.) under an atmosphere of argon. The mixture was heated to reflux for 24 h. The reaction mixture was cooled to room tem- perature, diluted with TH F, filtered through celite and concentrated in vacuo. The crude product was purified by column chromatography (silica gel, DCM/petrol ether 2:1→ 1 :1→ DCM) to afford compound 1 a (63.4 mg, 215 μιτιοΙ, 86 %) as yellow crystals (m.p. 257 °C). ¹H NMR

(300.13 MHz, C₄D₈0) 5 (ppm) = 8.29 (d, ³J = 8.7 Hz, 2 H, H7), 8.16 (d, ³J = 8.7 Hz, 2 H , H6), 7.86 (dd, ³J = 3.7 Hz, ⁴J = 1 .1 Hz, 2 H, H3), 7.57 (dd, ³J = 5.1 Hz, ⁴J = 1 .1 Hz, 2 H , H1 ), 7.15 (dd, ³J = 5A Hz, ³J = 3.7 Hz, 2 H, H2). ¹³C{¹H} N M R (75.48 MHz, C₄D₈0) δ (ppm) = 153.46 (OS), 146.16 (C4), 144.05 (C8), 138.10 (C7), 130.34 (C1 ), 129.02 (C2), 127.53 (C3), 122.13 (C6). H R-MS (H R-EI) [M]⁺= Ci₆Hi₀N₂S2, calcd.: 294.0285, found: 294.0289, diff.: +0.4 mmu. Elemental Analysis C16H10N2S2, calcd.: C 65.28, H 3.42, N 9.52, S 21.78, found: C 65.00, H 3.37, N 9.36, S 21 .59.

Example 3

Preparation of compound 1 b

(2b)

A flame dried Schlenk flask was charged with compound 3a (50.0 mg, 251 pmol), bis(triphenyl- phosphine)palladium(ll) dichloride (35.2 mg, 50.2 μιηοΙ), 5-hexyl-2-(tributylstannyl)thiophene (310 mg, 678 pmol), lithium chloride (63.8 mg, 1.51 mmol) and dry THF (2 mL) under an atmosphere of argon. The mixture was heated to reflux for 24 h. Then the reaction mixture was cooled to room temperature, diluted with THF, filtered through celite and concentrated in vacuo. The crude product was purified by column chromatography (silica gel, PE→ DCM/petrol ether 1 : 1 ) to afford compound 1 b (97.8 mg, 21 1 pmol, 84 %) as yellow crystals (m.p. 132 °C). ¹H NMR (300.13 MHz, CDCb) δ (ppm) = 8.25 (d, ³J = 8.7 Hz, 2 H, H13), 7.92 (d, ³J = 8.7 Hz, 2 H, HI 2), 7.53 (d, ³J = 3.7 Hz, 2 H, H9), 6.83 (d, ³J = 3.7 Hz, 2 H, H3), 2.87 (t, ³J = 7.5 Hz, 4 H, H5), 1 .80- 1.67 (m, 4 H, H5), 1.46-1.27 (m, 12 H, H2,3,4), 0.90 (t, ³ = 7.1 Hz, 6 H, HI ). ¹³C{¹H} NMR

(75.48 MHz, C₄D₈0) δ (ppm) = 152.41 (C1 1), 150.61 {CI), 143.01 (C14), 142.04 (C10), 137.09 (C13), 126.36 (C9), 125.63 (C8), 121.02 (C12), 31.72, 31 .66, 30.70 (C6), 28.90, 22.72, 14.22 (C1 ). HR-MS (HR-ESI) [M+H]⁺= C28H35N2S2, calcd.: 463.2236, found: 463.2239, diff.: +0.3 mmu. Elemental Analysis C28H34N2S2, calcd.: C 72.68, H 7.41 , N 6.05, S 13.86; found: C 72.76, H 7.42, N 5.95, S 13.69. Example 4

Preparation of compound 1 c

A flame dried Schlenk flask was charged with compound 3a (100 mg, 502 pmol), bis(triphenyl- phosphine)palladium(l l) dichloride (70.5 mg, 100 pmol), 5-Hexyl-5'-(tributylstannyl)-2,2'-bi- thiophene (732 mg, 1 .36 mmol), lithium chloride (128 mg, 3.01 mmol) and dry THF (4 mL) under an atmosphere of argon. The mixture was heated to reflux for 48 h. Then the reaction mixture was cooled to room temperature, diluted with THF, filtered through celite and concentrated in vacuo. The crude product was purified by column chromatography (silica gel, DCM) to afford compound 1 c (140 mg, 225 pmol, 44 %) as orange crystals and 137 mg monocoupling product (contaminated with BusSnCI). The monocoupling product was used again in a coupling reaction and yielded 98.0 mg (156 pmol) product. Total yield: 238 mg, 380 Mmol, 76 % (m.p. 184 °C). ¹ H N M R (400.18 MHz, CDCI3) δ (ppm) = 8.28 (d, ³J = 8.8 Hz, 2 H , H17), 7.96 (d, ³J = 9.0 Hz, 2 H , H16), 7.60 (d, ³J = 3.9 Hz, 2 H , H13, 7.15 (d, ³J = 3.9 Hz, 2 H , H12), 7.13 (d, ³J = 3.5 Hz, 2 H , H9), 6.73 (d, ³J = 3.4 Hz, 2 H, H8), 2.82 (t, ³J = 7.6 Hz, 4 H, H6), 1 .75-1 .65 (m, 4 H, H5), 1.45-1.27 (m, 12 H, H2,3,4), 0.90 (t, ³ = 6.7 Hz, 6 H , H1 ). ³C{ H} N M R (100.63 MHz, CDCI3) δ (ppm) = 152.1 1 (C15), 146.60 {CI), 143.19 (C18), 142.49, 141 .84, 137.08 (C17), 134.83 (C10), 127.16 (C13), 125.21 {CSS), 124.34 (C9), 123.99 (C1 6), 121 .13 (C12), 31 .72 (2 C), 30.40 (C6), 28.92 (C4), 22.73, 14.24 (C1 ). H R-MS (H R-ESI) [M+H]⁺=

calcd.: 626.1917, found: 626.1938, diff.: +2.1 mmu.

Example 5

Preparation of an OLED device comprising an emission layer which comprises lr(ppy)3 as emitting material and compound 1 b as semiconducting material An organic light-emitting diode (OLED) device was fabricated on an indium tin oxide (ITO) coated glass substrate (R_n ~ 13 Ω/°) that had been structured using hydrochloric acid. The substrate was cleaned with acetone and isopropanol for 15 min in an ultrasonic bath. Afterwards the substrate was exposed to oxygen plasma for 2 min in order to remove organic residues. Then the sample was moved to a glovebox with nitrogen atmosphere and kept there for the re- maining fabrication and characterization process.

The device comprise 10 nm M0O3 for enhanced hole injection, followed by 20 nm tris(4-carba- zol-9-yl-phenyl)amine (TCTA) as an electron blocking layer and a 40nm compound 1 b : tris(2- phenylpyridinato-C2,N)iridium(l ll) (lr(ppy)3), a triplett-emitter, (doping concentration 10wt.%) emission layer. The device was capped by a 1 ,3,5-tris(N-phenyl-2-benzimidazolyl)benzene

(TPBi) (20nm) hole blocking layer and a LiF / Al (0.7 nm / 200 nm) counter electrode. All thermal evaporation steps were done in a high vacuum chamber (10^"6 mbar).

The structure of the device is depicted in Figure 1

The OLED current density-voltage (J-V) characteristics were recorded with a source measure unit (Keithley 238). The current density-voltage curve for the OLED device comprising lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 2. The device luminance was calculated from the emission spectrum. The respective spectrometer had been calibrated with a secondary standard calibration halogen lamp (Philips FEL-1000W). Current efficiencies (cd/A) and power efficiencies (Im/W) were calculated from the electrical and optical properties. For this calculation a lambertian light distribution is assumed.

The luminance-current density curve for the OLED device comprising lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 3.

The power efficiency-luminance curve for the OLED comprising compound 1 b as lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 4. The current efficiency-luminance curve for the OLED device comprising lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 5.

Example 6

Preparation of compound 1d

(3a) (1 d) Preparation of compound 7a

A 1 M solution of compound 8a in DMF was cooled to 0 °C in the absence of light and NBS (1.0 eq.) was added. The mixture was allowed to warm to room temperature, stirred overnight and then diluted with DCM . The solution was extracted with H₂0 and brine. The combined aqueous layers were extracted with DCM. The combined organic layers were dried over MgSC and the solvent was removed in vacuo. The resulting light yellow oil was purified via column chromatography (silica gel, petroleum ether) yielding compound 7a as a colorless oil (99%). H NMR (300.13 MHz, CDCI₃) δ (ppm) = 7.18 (d, ³J = 5.5 Hz, 1 H, H9), 6.79 (d, ³J = 5.5 Hz, 1 H, H8), 2.56 (t, ³J = 7.7 Hz, 2 H, H6), 1.63-1.51 (m, 2 H , H5), 1.40-1.24 (m, 6 H, H4-2), 0.89 (t, ³J = 6.8 Hz, 3 H, H1).

Preparation of compound 1d

A suspension of magnesium turnings (3.3 eq) in dry diethylether was stirred for 1 h under an argon atmosphere. Compound 7a (3 eq) was added. The Grignard reaction was initiated by careful heating of the solution accompanied by a change of color to brown and tarnishing. When the exothermic reaction was completed, the reaction mixture was heated to reflux for 1 h. After cooling to room temperature compound 3a (1 eq) and Ni(dppp)Cl2 (2 mol%) were added and the solution was heated to reflux overnight. The completion of the reaction was checked via TLC. Then the mixture was quenched with water. The organic phase was separated and the aqueous layer was extracted with DCM. The combined organic layers were dried over MgS04 and the solvent was removed under reduced pressure. Compound 1 d was purified via column chromatography, yielding yellow crystals. ¹H NMR (300.13 M Hz, CDCI₃) δ (ppm) = 8.34 (d, ³ J = 8.7 Hz, 2 H, H13), 7.89 (d, J = 8.7 Hz, 2 H, H12), 7.37 (d, ³J = 5.1 Hz, 2 H, H1 1 ), 7.04 (d, ³J = 5.1 Hz, 2 H, H9), 3.06 (t, ³J = 7.9 Hz, 4 H, H6), 1.80-1.65 (m, 4 H, H5), 1.47-1.23 (m, 12 H, H2-4), 0.87 (t, ³ J = 7.0 Hz, 6 H, /-/1 ).

Example 7

Preparation of compound 7b

A 1 M solution of compound 8b in DMF was cooled to 0 °C in the absence of light and NBS (1.0 eq.) was added. The mixture was allowed to warm to room temperature, stirred overnight and then diluted with DCM . The solution was extracted with H₂0 and brine. The combined aqueous layers were extracted with DCM . The combined organic layers were dried over MgSC and the solvent was removed in vacuo. The resulting light yellow oil was purified via column chromatography (silica gel, petroleum ether) yielding compound 7b as a colorless oil (99%). H NMR (300.13 MHz, CDCI₃) δ (ppm) = 7.18 (d, ³J = 5.6 Hz, 1 H, H1 1), 6.79 (d, ³J = 5.6 Hz, 1 H, H12), 2.56 (t, ³J = 7.7 Hz, 2 H, H8), 1.64-1.50 (m, 2 H, H7), 1.39-1 .21 (m, 10 H, H6-2), 0.88 (t, ³J = 6.7 Hz, 3 H, H1 ).

Preparation of compound 1e

A suspension of magnesium turnings (3.3 eq) in dry diethylether was stirred for 1 h under an argon atmosphere. Compound 7b (3 eq) was added. The Grignard reaction was initiated by careful heating of the solution accompanied by a change of color to brown and tarnishing. When the exothermic reaction was completed, the reaction mixture was heated to reflux for 1 h. After cooling to room temperature compound 3a (1 eq) and Ni(dppp)CI₂ (2 mol%) were added and the solution was heated to reflux overnight. The completion of the reaction was checked via TLC. Then the mixture was quenched with water. The organic phase was separated and the aqueous layer was extracted with DCM. The combined organic layers were dried over MgSC and the solvent was removed under reduced pressure. Compound 1 e was purified via column chroma- tography, yielding yellow crystals. ¹H NMR (300.13 M Hz, CDCI3) δ (ppm) = 8.34 (d, ³ J = 8.7 Hz, 2 H, H15), 7.89 (d, J = 8.7 Hz, 2 H, H ), 7.37 (d, ³J = 5.1 Hz, 2 H, H1 1 ), 7.04 (d, J = 5.1 H, H10), 3.06 (t, J = 7.8 Hz, 4 H, H8), 1.79-1 .65 (m, 4 H, 7), 1.45-1 .20 (m, 20 H, H2-6), 0.87 (t, J = 6.8 Hz, 6 H, Ηλ).

Example 8

Preparation of polymer Pa

Preparation of compound 9a

To a solution of compound 1 e (0.3 M) in a 1 :1 mixture of DMF and DCM NBS (2 eq.) was added in the absence of light. The mixture was stirred overnight and poured into H2O (150 ml_). The aqueous layer was extracted three times with Et₂0. The combined organic layers were dried over MgS0₄, and the solvent was removed in vacuo. The resulting orange oil was purified via column chromatography (silica gel, petroleum ether/DCM 3:1 ) yielding compound 9a as yellow crystals. ¹H NMR (300.13 MHz, CDCI₃) δ (ppm) = 8.31 (d, = 8.8 Hz, 2 H, HI 5), 7.81 (d, J = 8.8 Hz, 2 H, HI4), 6.99 (s, 2 Η, HIO), 2.97 (t, ³J = 7.8 Hz, 4 H, H8), 1.76-1.62 (m, 4 Η, H7), 1.46-1.19 (m, 20 Η, H2-6), 0.87 (t, J = 6.5 Hz, 6 H, HI ).

Preparation of polymer Pa

Cyclooctadien (COD, 2.25 eq.) and Bis(1 ,5-cyclooctadiene)nickel(0) (2.25 eq.) were dissolved in DM F (0.5 M) under argon atmosphere. 2,2'-Bipyridine (2.25 eq) was added and the color of the solution turned to deep blue. To activate the catalyst, the solution was heated to 50 °C for 30 minutes. Afterwards a solution of compound 9a in THF (0.25 M) was added carefully. The resulting reaction mixture was heated to 60 °C for 30 h. After completion of the reaction 0.01 eq. of endcapper (bromobenzene) were added and the mixture was heated to 60 °C for 2 additional hours. The reaction mixture was poured into a 1 :2 mixture of hydrochloric acid and methanol. The resulting suspension was transferred into a soxhlet extractor and successively extracted with methanol, aceton and chloroform. Evaporation of the solvent of the chloroform fraction yielded 7% of a red polymer Pa. The average molecular weight was estimated to be

7.51*10² g/mol with a polydispersity (M_w/M_n) of 3.67. Example 9

Preparation of compound 9b

To a solution of compound 1 d (0.3 M) in a 1 :1 mixture of DMF and DCM NBS (2 eq.) was added in the absence of light. The mixture was stirred overnight and poured into H₂0 (150 ml_). The aqueous layer was extracted three times with ΕΪ20. The combined organic layers were dried over MgS0₄, and the solvent was removed in vacuo. The resulting orange oil was purified via column chromatography (silica gel, petroleum ether/DCM 3:1 ) yielding compound 9b yellow crystals. Ή NMR (300.13 MHz, CDCI₃) δ (ppm) = 8.32 (d, J = 9.0 Hz, 2 H, HI 3), 7.81 (d, J = 8.8 Hz, 2 H, HI2), 6.99 (s, 2 Η, H8), 2.97 (t, ³J = 7.8 Hz, 4 H, H6), 1 .76-1.62 (m, 4 H, H5), 1.47-1.23 (m, 12 H, H2-4), 0.88 (t, ³J = 7.0 Hz, 6 H, HI ).

Claims

1. Compounds of formula

wherein

p is 1 , 2, 3, 4, 5 or 6,

n is 0, 1 or 2,

q is 0, 1 , 2, 3, 4, 5 or 6, selected from the group consisting of

wherein R⁵⁰ and R⁵¹ are independently from each other H, Ci-₂o-alkyl, C(0)-Ci-₂o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci-₂₀-alkyl, C(0)-0-C₂-io-alkenyl or C(0)-0-phenyl, Ar¹ is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of d-20-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br, wherein Ci_₂o-alkyl, Ci-₂o-alkyl, 0-Ci_₂o-alkyl, C(0)-Ci_₂o-alkyl and C(0)-0-Ci_₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

Ar² is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-₂₀-alkyl, O-Ci-₂₀-alkyl, C(O)-Ci-₂₀-alkyl, C(O)-O-Ci-₂₀-alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-₂o-alkyl and C(0)-0-Ci-₂o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

2. The compounds of claim 1 wherein the compound of formula (1 ) are of formula

wherein p, n, q, L¹, and Ar² are as defined for the compound of formula (1 ) in claim 1. 3. The compounds of claim 1 or claim 2 wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 ) ■ (A2) , (A3) , (A4)

(A5) ' (A6)

(B9) (B10) wherein

X is O, S, Se or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-₁₀-alkyl or phenyl, and

Y is at each occurrence CH or N .

4. The compounds of claim 1 or claim 2, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 ) (A2a) (A3a) (A4a)

(A5a) ' (A6a)

(B5a) (B6a) (B7a) (B8a)

(B9a) (B10a) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci-10-alkyl or phenyl, and

Y is at each occurrence CH or N .

5. The compounds of claimi or claim 2, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 ) (B1 ) (B2) wherein

X is O, S or N-R¹⁰⁰,

wherein R¹⁰⁰ is Ci_io-alkyl or phenyl, and

Y is at each occurrence CH or N .

6. The compounds of claim 1 or claim 2, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of

(A1 a) (B1a) wherein

Y is at each occurrence CH or N

The compounds of claim 1 or claim 2, wherein the 5 to 9 membered heteroaromatic moiety is

(A1 b) (B1 b)

8. The compounds of any of claims 1 to 7, wherein L¹ is selected from the group consisting of

9. The compounds of claim 8 wherein L¹ is

wherein R⁵⁰ and R⁵¹ are H .

10. The compounds of any of claim 1 to 9, wherein Ar² is a Ce-14-aromatic moiety selected from the group consisting of

wherein Ci-₂o-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,

wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl. 1 1. The compounds of any of claims 1 to 10, wherein

p is 1 , 2 or 3, n is 0 or 1 , and

q is 0, 1 , 2 or 3.

12. The compounds of claim 1 1 , wherein

p is 1 or 2,

n is 0, and

q is 0 or 1.

13. The compounds of claim 12, wherein

p is 1 or 2,

n is 0, and

q is 0.

A process for the preparation of the compounds of formula (1 ) of any of claims 1 to 13, which process comprises the step of treating a compound of formula

(3) wherein Z¹ is CI, Br, I or OS0₂CF₃, with a compound of formula

(2) wherein p, n, q, L¹, Ar¹ and Ar² are as defined for the compound of formula (1 ) and R⁷⁰ alkyl, in the presence of catalyst I. 15. A process for preparation of the compounds of formula (1 ) of any of claim 1 to 13, which process comprises the step of treating a compound of formula

(3)

wherein Z¹ is CI, Br, I or OS0₂CF₃ with a compound of formula

(7')

wherein p, n, q, L¹, Ar¹ and Ar² are as defined for the compound of formula (1 ), and Z² is CI, Br, I

in the presence of catalyst 1

Polymers comprising a unit of formula

(10) wherein p, n, q, L¹, Ar¹ and Ar² are as defined in claim 1.

17. A process for the preparation of a polymer of claim 16, which process comprises the step of treating a compound of formula

(9) wherein p, n, q, L¹, Ar¹ and Ar² are as defined in claim 1 , and Z³ is CI, Br or I, with catalyst III.

18. Compounds of formula

(9) wherein p, n, q, L¹, Ar¹ and Ar² are as defined in claim 1 , and Z³ is CI, Br or I. 19. An electronic device comprising the compounds of any of claims 1 to 13 or the polymer of claim 16.

Use of the compounds of any of claim 1 to 13 or the polymer of claim 16 as semiconducting materials.