Spirobifluorene compounds for organic electroluminescent devices

Patent metadata

Field	Value
Publication number	US-9812648-B2
Application number	US-201314378529-A
Country	US
Kind code	B2
Filing date	Jan 21, 2013
Priority date	Feb 14, 2012
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

Spirobifluroene compounds of the formula (1) which are suitable for use in electronic devices,

and in particular organic electroluminescent devices, and to electronic devices that include the spirobifluorene compounds.

First claim

The invention claimed is:

1. A compound of the formula

where the following applies to the symbols and indices used:
Ar 1 is selected from the group consisting of fluorene, biphenyl, terphenyl, quaterphenyl, dibenzofuran and dibenzothiophene, each of which is optionally substituted by one or more radicals R 5 ;
Ar 2 is selected from any one of formulae (11) to (27)

where the dashed bond indicates the bond to the nitrogen, and the groups are optionally substituted by one or more radicals R 5 ;
R 1 , R 2 , R 3 , R 4 are on each occurrence, identically or differently, selected from the group consisting of H, D, F, Cl, Br, I, CN, Si(R 6 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms, and a branched alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, and a cyclic alkyl group having 3 to 40 C atoms, each of which optionally is substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2 groups optionally is replaced by Si(R 6 ) 2 , C═NR 6 , P(═O)(R 6 ), SO, SO 2 , NR 6 , O, S or CONR 6 and where one or more H atoms optionally is replaced by D, F, Cl, Br or I, an aromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R 6 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which optionally is substituted by one or more radicals R 6 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 , where two or more adjacent substituents R 1 or R 2 or R 3 or R 4 may optionally form a mono- or polycyclic, aliphatic ring system, which optionally is substituted by one or more radicals R 6 ;
R 5 is on each occurrence, identically or differently, selected from the group consisting of H, D, F, Cl, Br, I, CN, Si(R 6 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched alkyl, alkoxy, and thioalkyl group having 3 to 40 C atoms, and a cyclic alkyl group having 3 to 40 C atoms, each of which optionally is substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2 groups optionally is replaced by Si(R 6 ) 2 , C═NR 6 , P(═O)(R 6 ), SO, SO 2 , NR 6 , O, S or CONR 6 and where one or more H atoms optionally is replaced by D, F, Cl, Br or I, an aromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R 6 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which optionally is substituted by one or more radicals R 6 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 ;
R 6 is selected from H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic, or heteroaromatic, ring system having 5 to 30 C atoms, in which one or more H atoms optionally is replaced by D or F, where two or more adjacent substituents R 6 may form a mono- or polycyclic, aliphatic ring system with one another;
m is 0, 1 or 2;
n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; and
r, s are on each occurrence, identically or differently, 0, 1, 2, 3 or 4.

2. The compound according to claim 1 , wherein Ar 2 is selected from the groups of formulae (11), (20) or (24), which are optionally substituted by one or more radicals R 5 .

3. The compound according to claim 1 , wherein the groups Ar 1 and Ar 2 are different from one another.

4. The compound according to claim 1 , wherein R 1 to R 4 are selected, identically or differently on each occurrence, from the group consisting of H, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, a branched alkyl or alkoxy group having 3 to 10 C atoms, and a cyclic alkyl group having 3 to 10 C atoms, each of which optionally is substituted by one or more radicals R 6 , where one or more non-adjacent CH 2 groups optionally is replaced by O and where one or more H atoms optionally is replaced by F, and an aromatic ring system having 6 to 24 aromatic ring atoms, which may in each case he substituted by one or more radicals R 6 .

5. The compound according to claim 1 , wherein the radical R 5 which is bonded to Ar 1 or Ar 2 is identically or differently on each occurrence, selected from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, and an aromatic system having 5 to 24 aromatic ring atoms, each of which optionally is substituted by one or more radicals R 6 .

6. The compound according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 are on each occurrence, identically or differently, selected from the group consisting of H, D, F, Cl, Br, I, CN, Si(R 6 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms, a branched alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, and a cyclic alkyl group having 3 to 40 C atoms, each of which optionally is substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2 groups optionally is replaced by Si(R 6 ) 2 , C═NR 6 , P(═O)(R 6 ), SO, SO 2 , NR 6 , O, S or CONR 6 and where one or more H atoms optionally is replaced by D, F, Cl, Br or I, an aromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R 6 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which optionally is substituted by one or more radicals R 6 , and an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 ; and
R 6 is selected from H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, in which one or more H atoms optionally is replaced by D or F.

7. A process for the preparation of the compound according to claim 1 , which comprises introducing the diarylamino group —NAr 1 Ar 2 by a C—N coupling reaction between
a 1- or 3- or 4-halogenated spirobifluorene of the formula

 wherein X is halogen, and
a diarylamine of the formula HNAr 1 Ar 2 .

8. An electronic device which comprises the compound according to claim 1 .

9. The electronic device as claimed in claim 8 , wherein the device is selected from the group consisting of an organic clectroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic dye-sensitised solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell, an organic laser diode and an organic plasmon emitting device.

10. An organic electroluminescent device which comprises the compound according to claim 1 comprised as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer, or as matrix material for fluorescent or phosphorescent emitters in an emitting layer.

Assignees

• Merck Patent Gmbh

Inventors

• Montenegro Elvira
• Parham Amir H
• Stoessel Philipp
• Mujica-Fernaud Teresa
• Voges Frank
• Buesing Arne

Classifications

• C09K2211/1007

  Non-condensed systems · CPC title

• C07D209/86

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system · CPC title

• C07D333/76

  Dibenzothiophenes · CPC title

• C07D209/88

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system · CPC title

• C09K2211/1011

  Condensed systems · CPC title