IP Library Granted Patent US 10,128,448
Granted Patent B2
US 10,128,448 · App. 14/786,507 · Granted Nov 13, 2018

Transition metal complexes with carbene ligands and the use thereof in OLEDs

Inventors: Stefan Metz (Mannheim, DE); Thomas Geβner (Heidelberg, DE); Korinna Dormann (Bad Dürkheim, DE); Glauco Battagliarin (Mannheim, DE); Peter Murer (Oberwil, CH); Ute Heinemeyer (Neustadt, DE); Christian Lennartz (Schifferstadt, DE); Gerhard Wagenblast (Wachenheim, DE)
Assignee: UDC Ireland Limited
H01L51/0085C07F15/0033C07F15/0086C09B57/00C09B57/10C09K11/025C09K11/06H01L27/3206H01L51/0087C09K2211/185H01L51/5012H01L51/5016H01L51/5056H01L51/5072H01L51/5096Y02E10/549
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Quick Facts
Patent No.
US 10,128,448
App. No.
14/786,507
Granted
Nov 13, 2018
Kind
B2
Abstract

The present invention relates to iridium and platinum carbene complexes of the general formula (I), to OLEDs (Organic Light-Emitting Diodes) which comprise such complexes, to a device selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, to the use of such a metal-carbene complex in OLEDs, for example as emitter, matrix material, charge transport material and/or charge or exciton blocker.

Claims (207)

1. A metal-carbene complex of the general formula

wherein

M is Ir or Pt,

R 1 and R 2 are independently of each other a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 ring atoms,

A 1 , A 2 , A 3 and A 4 are independently from each other CR 3 or N;

each R 3 is independently of each other H, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 ring atoms; or a group with donor or acceptor action;

K and L are independently from each other a bidentate monoanionic ligand;

for M is Ir, o is 1, 2 or 3, m is 0, 1, or 2, n is 0, 1, or 2 and m+n+o=3 and

for M is Pt, o is 1, or 2, m is 0, or 1, n is 0, or 1 and m+n+o=2.

2. The metal-carbene complex according to claim 1 , which is a metal-carbene complex of the general formula

wherein

A 1 is N, or CR 4 ,

R 4 , R 5 , R 6 and R 7 are independently of each other H, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 ring atoms; or a group with donor or acceptor action and

R 1 , R 2 , M, L, n, m and o are as defined in claim 1 .

3. The metal complex according to claim 2 , which is a metal-carbene complex of the general formula

wherein

K is a bidentate monoanionic ligand of formula

in which R 74 and R 74′ are in each case independently a linear or branched alkyl radical having 1 to 6 carbons atoms optionally bearing at least one functional group; substituted or unsubstituted cycloalkyl radical having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 20 carbon atoms; substituted or unsubstituted heteroaryl radical having a total of 5 to 18 ring atoms, and

R 75 is hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 20 carbon atoms;

A 1 is N, or CR 4 ,

R 4 , R 5 , R 6 and R 7 are independently of each other H, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 12 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 15 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 15 ring atoms; or a group with donor or acceptor action, selected from halogen radicals, SiMe 3 , SiPh 3 , OMe, NO 2 , CN, NCO, NCS, CF 3 , and

R 1 and R 2 are independently of each other a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally beating at least one functional group and having 3 to 12 carbon atoms, substituted or unsubstituted aryl radical, optionally bearing at least one functional group and having 6 to 15 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 15 carbon atoms.

4. The metal complex according to claim 2 , which is a metal-carbene complex of the general formula

wherein

o is 1, 2, or 3,

L is a bidentate monoanionic ligand of formula

in which R 74 and R 74′ are in each case independently a linear or branched alkyl radical having 1 to 6 carbons atoms optionally bearing at least one functional group; substituted or unsubstituted cycloalkyl radical having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical having 6 to 20 carbon atoms; substituted or unsubstituted heteroaryl radical having a total of 5 to 18 ring atoms, and

R 75 is hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 20 carbon atoms; or

L is a bidentate monoanionic ligand of formula

A 1 is N, or CR 4 ,

R 4 , R 5 , R 6 and R 7 are independently of each other H, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 12 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 15 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 15 ring atoms; or a group with donor or acceptor action, selected from halogen radicals, SiMe 3 , SiPh 3 , OMe, NO 2 , CN, NCO, NCS, CF 3 , and

R 1 and R 2 are independently of each other a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally beating at least one functional group and having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 12 carbon atoms, substituted or unsubstituted aryl radical, optionally bearing at least one functional group and having 6 to 15 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 15 ring atoms.

5. The metal complex according to claim 4 , which is a metal-carbene complex of the general formula

wherein

R 1 , R 2 , R 5 , R 6 , R 7 , and A 1 are as defined in claim 4 .

6. The metal complex according to claim 2 , wherein R 7 is hydrogen.

7. The metal complex according to claim 2 , wherein

A 1 is CR 4 , wherein R 4 is hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 15 carbon atoms, or a group with donor or acceptor action selected from CN, CF 3 , SiMe 3 , halogen radicals.

8. The metal complex according to claim 2 , wherein

R 5 is hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 15 carbon atoms, or a group with donor or acceptor action selected from CN, CF 3 , SiMe 3 , halogen radicals.

9. The metal complex according to claim 2 , wherein

R 6 is hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, substituted or unsubstituted aryl radical having 6 to 15 carbon atoms, or a group with donor or acceptor action selected from CN, CF 3 , SiMe 3 , halogen radicals.

10. The metal-carbene complex according to claim 1 , wherein

R 1 is a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 ring atoms.

11. The metal-carbene complex according to claim 1 , wherein

R 2 is a linear or branched alkyl radical having 1 to 6 carbons atoms, or a unsubstituted aryl radical having 6 to 15 carbon atoms.

12. The metal-carbene complex according to claim 1 , which is a compound of formula

Compound

R 1

R 2

R 6

EM-1

CH 3

H

EM-2

CH 3

H

EM-3

CH(CH 3 ) 2

H

EM-4

CH(CH 3 ) 2

H

EM-5

CH(CH 3 ) 2

H

EM-6

CH(CH 3 ) 2

H

EM-7

CH(CH 3 ) 2

H

EM-8

CH(CH 3 ) 2

H

EM-9

CH 3

H

EM-10

CH 3

H

EM-11

CH 3

H

EM-12

CH 3

H

EM-13

H

EM-14

H

EM-15

H

EM-16

H

EM-17

H

EM-18

H

EM-19

CH(CH 3 ) 2

F

EM-20

CH(CH 3 ) 2

F

EM-21

CH(CH 3 ) 2

F

EM-22

CH(CH 3 ) 2

F

EM-23

CH(CH 3 ) 2

F

EM-24

CH(CH 3 ) 2

F

EM-25

CH 3

F

EM-26

CH 3

F

EM-27

CH 3

F

EM-28

CH 3

F

EM-29

CH 3

F

EM-30

CH 3

F

EM-31

F

EM-32

F

EM-33

F

EM-34

F

EM-35

F

EM-36

F

EM-37

CH(CH 3 ) 2

CF 3

EM-38

CH(CH 3 ) 2

CF 3

EM-39

CH(CH 3 ) 2

CF 3

EM-40

CH(CH 3 ) 2

CF 3

EM-41

CH(CH 3 ) 2

CF 3

EM-42

CH(CH 3 ) 2

CF 3

EM-43

CH 3

CF 3

EM-44

CH 3

CF 3

EM-45

CH 3

CF 3

EM-46

CH 3

CF 3

EM-47

CH 3

CF 3

EM-48

CH 3

CF 3

EM-49

CF 3

EM-50

CF 3

EM-51

CF 3

EM-52

CF 3

EM-53

CF 3

EM-54

CF 3 .

13. An organic electronic device, comprising at least one metal-carbene complex according to claim 1 .

14. The organic electronic device according to claim 13 , wherein the organic electronic device is selected from organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic field-effect transistors (OFETs) and light-emitting electrochemical cells (LEECs).

15. A light-emitting layer comprising at least one metal-carbene complex according to claim 1 .

16. The light-emitting layer according to claim 15 , further comprising a host material.

17. An apparatus selected from the group consisting of stationary visual display units, illuminations, information panels, and mobile visual display units, illumination units; keyboards; items of clothing; furniture and wallpaper, comprising the organic electronic device according to claim 13 .

18. A method of using the metal-carbene complex according to claim 1 , comprising:

adding the metal-carbene complex to electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices.

19. A process for preparing a metal-carbene complex according to claim 1 by contacting a suitable compound comprising M with a compound of the general formula

wherein

A 1 , A 2 , A 3 , A 4 , R 1 , R 2 and M are as defined in claim 1 , and

X is F, CA, Br, I, PF 6 , or BF 4 .

20. An apparatus selected from the group consisting of stationary visual display units, illuminations, information panels, and mobile visual display units, illumination units; keyboards; items of clothing; furniture and wallpaper, comprising the light-emitting layer according to claim 15 .

Assignments (3)
CORRECTIVE ASSIGNMENT TO CORRECT THE INCORRECT APPL. NO. 14/901,736 PREVIOUSLY RECORDED AT REEL: 039460 FRAME: 0615. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 8, 2017
From: BASF SE
To: UDC IRELAND LIMITED
Reel/Frame 042740/0222 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 25, 2016
From: BASF SE
To: UDC IRELAND LIMITED
Reel/Frame 039460/0615 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 17, 2016
From: METZ, STEFAN; GESSNER, THOMAS; DORMANN, KORINNA; BATTAGLIARIN, GLAUCO; MURER, PETER; HEINEMEYER, UTE; LENNARTZ, CHRISTIAN; WAGENBLAST, GERHARD
To: BASF SE
Reel/Frame 038946/0655 →
Priority Claims (1)
EP 13165738 · Apr 29, 2013 · regional
Continuity (1)
Related Publication 20160072081A1 · Mar 10, 2016
Cited By (1)
US 12,382,824