Silyl- and heteroatom-substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzophospholes, and use thereof in organic electronics

Patent metadata

Field	Value
Publication number	US-9458182-B2
Application number	US-200913143651-A
Country	US
Kind code	B2
Filing date	Dec 14, 2009
Priority date	Jan 7, 2009
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

The present invention relates to silyl- and heteroatom-substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and disilylbenzophospholes of the formula (I) or (I*), to the use of the compounds of the formula (I) or (I*) in organic electronics applications, preferably in organic light-emitting diodes, to an organic light-emitting diode comprising at least one compound of the formula (I) or (I*), to a light-emitting layer comprising at least one compound of the formula (I) or (I*), to a blocking layer for holes/excitons comprising at least one compound of the formula (I) or (I*), and to an apparatus selected from the group consisting of stationary visual display units, mobile visual display units, illumination units, keyboards, items of clothing, furniture and wallpaper, comprising at least one inventive organic light-emitting diode.

First claim

The invention claimed is:

1. A compound of formula (Ia), (Ib), (Ic), (Id), or (Ie)

wherein
X is NR, S, or O;
R is aryl;
A is —NR 6 R 7 or —P(O)R 8 R 9 ;
R 1 , R 2 , and R 3 are each independently aryl, alkyl, or a crosslinkable or polymerizable group attached via a spacer, where at least one of the R 1 , R 2 , and R 3 radicals comprises at least two carbon atoms, or OR 22 ;
R 4 and R 5 are each independently alkyl, aryl, or a crosslinkable or polymerizable group attached via a spacer, an A group, or a group with donor or acceptor action;
n and m are each independently 0, 1, 2, or 3;
R 6 and R 7 together with the nitrogen atom form a cyclic radical which has 3 to 10 ring atoms and is optionally unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and a group with donor or acceptor action, and/or optionally fused to one or more further cyclic radicals having 3 to 10 ring atoms, where the fused radicals are optionally unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a crosslinkable or polymerizable group attached via a spacer, and a group with donor or acceptor action;
R 22 is SiR 23 R 24 R 25 or a crosslinkable or polymerizable group attached via a spacer;
R 8 , R 9 , R 23 , R 24 , and R 25 are each independently aryl, heteroaryl, alkyl, cycloalkyl, heterocycloalkyl, or a crosslinkable or polymerizable group attached via a spacer;
the group with donor or acceptor action in R 4 , R 5 , R 6 , and R 7 is selected from the group consisting of C 1 - to C 20 -alkoxy, C 6 - to C 30 -aryloxy, a halogen radical, a halogenated C 1 - to C 20 -alkyl radical, amino, a pseudohalogen radical, —C(O)OC 1 - to C 4 -alkyl, and P(O)R 2 ; and
two units of formula (Ia), (Ib), (Ic), (Id), and (Ie) are optionally bridged to one another via a linear or branched, saturated or unsaturated bridge optionally interrupted by at least one heteroatom or via O, where the bridge in formula (Ia), (Ib), (Ic), (Id), and/or (Ie) is in each case attached to the silicon atoms instead of R 2 .

2. The compound of claim 1 , wherein the —NR 6 R 7 group is selected from the group consisting of pyrrolyl, 2,5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl, isoindolinyl, carbazolyl, azacarbazolyl, diazacarbazolyl, imidazolyl, benzimidazolyl, pyrazolyl, indazolyl, 1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, tetrazolyl, 1,3-oxazolyl, 1,3-thiazolyl, pentazolyl, piperidyl, morpholinyl, 1,4-oxazinyl, and 9,10-dihydroacridinyl, which are optionally unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and a group with donor or acceptor action.

3. The compound of claim 1 , wherein R 8 and R 9 are each independently aryl or heteroaryl, which are optionally unsubstituted or substituted by one or more substituents selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and a group with donor or acceptor action.

4. The compound of claim 1 , selected from the group consisting of

wherein
X is S or O, and
R′ is H or CH 3 .

5. The compound of claim 1 , wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 22 , R 23 , R 24 , and R 25 is independently a polymerizable or crosslinkable group which is attached via a spacer and is polymerizable or crosslinkable by a method selected from the group consisting of free-radical, cationic polyaddition, and coupling reaction.

6. The compound of claim 1 , wherein at least one of R 1 , R 2 , and R 3 is independently a polymerizable or crosslinkable group attached via a spacer.

7. The compound of claim 1 , wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 22 , R 23 , R 24 , and R 25 comprises at least one polymerizable or crosslinkable group selected from the group consisting of a C—C double bond, an acrylate, a methacrylate, oxetanyl, and 1,2-epoxy ether.

8. A process for preparing at least one compound of formula (Ia), (Ib), (Ic), (Id), and (Ie) of claim 1 , wherein the R, SiR 1 R 2 R 3 , and A radicals and, where present, R 4 and R 5 radicals are introduced into a base skeleton of formula (II)

wherein X is NR, S, or O,
the process comprising Variant a), b), c), or d):
Variant a)
ia) preparing a precursor compound suitable for introduction of the R 4 , R 5 , SiR 1 R 2 R 3 , and A radicals,
iia) introducing the R radical, and
iiia) introducing the R 4 and R 5 radicals, where present, and the SiR 1 R 2 R 3 and A radicals;
Variant b)
ib) introducing the R radical,
iib) preparing a precursor compound suitable for introduction of the R 4 , R 5 , SiR 1 R 2 R 3 , and A radicals, and
iiib) introducing the R 4 and R 5 radicals, where present, and the SiR 1 R 2 R 3 and A radicals;
Variant c)
ic) preparing a precursor compound suitable for introduction of the R 4 , R 5 , SiR 1 R 2 R 3 , and A radicals,
iic) introducing the R 4 and R 5 radicals, where present, and the SiR 1 R 2 R 3 and A radicals, and
iiic) introducing the R radical;
Variant d)
id) preparing a precursor compound suitable for introduction of the R 4 , R 5 , SiR 1 R 2 R 3 , and A radicals, and
iid) introducing the R 4 and R 5 radicals, where present, and the SiR 1 R 2 R 3 , and A radicals.

9. The process of claim 8 , wherein a halogen-metal exchange is performed on a halogenated base skeleton (II) in diethyl ether as a solvent.

10. The process of claim 9 , wherein a silane reactant is initially charged simultaneously with a halogenated base skeleton (II) and then a metal reagent is added.

11. The process of claim 8 , wherein a silane reactant is initially charged simultaneously with a halogenated base skeleton (H) and then a metal reagent is added.

12. A formulation, comprising a compound of formula (Ia), (Ib), (Ic), (Id), or (Ie) of claim 1 ,
wherein the formulation is suitable for a liquid-processed application in organic electronics.

13. A process for producing a crosslinked or polymerized material comprising at least one compound of formula (Ia), (Ib), (Ic), (Id), and (Ie) of claim 1 in crosslinked or polymerized form, the process comprising:
(i) preparing a crosslinkable or polymerizable compound of formula (Ia), (Ib), (Ic), (Id), or (Ie), wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 22 , R 23 , R 24 , and R 25 is a crosslinkable or polymerizable group attached via a spacer, and
(i

Assignees

• Langer Nicolle
• Schildknecht Christian
• Watanabe Soichi
• Fuchs Evelyn
• Wagenblast Gerhard
• Lennartz Christian
• Molt Oliver
• Dormann Korinna
• Loh Chuanjie
• Hunze Arvid
• Krause Ralf
• Schmid Guenter
• Heuser Karsten
• Van Elsbergen Volker
• Boerner Herbert Friedrich
• Kirsch Stefan
• Basf Se
• Oledworks Gmbh
• Osram Opto Semiconductors Gmbh

Inventors

• Langer Nicolle
• Schildknecht Christian
• Watanabe Soichi
• Fuchs Evelyn
• Wagenblast Gerhard
• Lennartz Christian
• Molt Oliver
• Dormann Korinna
• Loh Chuanjie
• Hunze Arvid
• Krause Ralf
• Schmid Guenter
• Heuser Karsten
• Van Elsbergen Volker
• Boerner Herbert Friedrich
• Kirsch Stefan

Classifications

• H01L51/5016

  Electricity · mapped topic

• C07F7/0854

  Chemistry & Metallurgy · mapped topic

• C07F7/0814 Primary

  said ring is substituted at a C ring atom by Si · CPC title

• H01L51/0072

  Electricity · mapped topic

• C07F9/65517

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title