IP Library › Granted Patent US 11,605,790

Granted Patent B2

US 11,605,790 · App. 16/853,032 · Granted Mar 14, 2023

Monosubstituted diazabenzimidazole carbene metal complexes for use in organic light emitting diodes

Inventors: Peter Murer (Oberwil, CH); Korinna Dormann (Bad Dürkheim, DE); Flavio Luiz Benedito (Ludwigshafen, DE); Glauco Battagliarin (Mannheim, DE); Stefan Metz (Mannheim, DE); Ute Heinemeyer (Neustadt, DE); Christian Lennartz (Schifferstadt, DE); Gerhard Wagenblast (Wachenheim, DE); Soichi Watanabe (Seoul, KR); Thomas Geßner (Heidelberg, DE)

Assignee: UDC Ireland Limited

H01L51/0085 C07F15/0033 C07F15/0086 C09B57/00 C09B57/10 C09K11/06 H01L51/0087 C09K2211/185 H01L51/5016 Y02E10/549

View Patent ↗

Loading inventors, assignments & file history…

Monitor This Case

Get email alerts when status or documents change.

Order Certified Copies

Most orders are placed with the USPTO same day — all within 24 business hours.

Order via The Patent Place →

Pre-filled with this patent's details

Quick Facts

Patent No.: US 11,605,790
App. No.: 16/853,032
Granted: Mar 14, 2023
Kind: B2

External Links

USPTO Patent Center↗ Full Patent PDF↗

Abstract

An organic electronic device, preferably an organic light-emitting diode (OLED), comprising at least one metal-carbene complex comprising one, two or three specific bidentate diazabenzimidazole carbene ligands; a light-emitting layer comprising said metal-carbene complex as emitter material, preferably in combination with at least one host material; the use of said metal-carbene complex in an OLED; an apparatus selected from the group consisting of stationary visual display units, mobile visual display units, illumination units, units in items of clothing, units in handbags, units in accessories, units in furniture and units in wallpaper comprising said organic electronic device, preferably said OLED, or said light-emitting layer; the metal-carbene complex comprising one, two or three specific bidentate diazabenzimidazole carbene ligands mentioned above and a process for the preparation of said metal-carbene complex.

Claims (834)

1. An organic electronic device comprising at least one metal-carbene complex, wherein the metal is Ir or Pt, comprising one, two or three bidentate ligands of formula (I) and/or (I′)

wherein

R 1 has the following meaning:

wherein:

m is 1;

˜ is the bonding site to the ligand of formula (I) or (I′); and

the group R 1 has one of the following definitions:

R 6

R 7

R 8

iso-butyl

methyl

hydrogen

tert-butyl

methyl

hydrogen

iso-butyl

ethyl

hydrogen

tert-butyl

ethyl

hydrogen

iso-propyl

n-propyl

hydrogen

iso-butyl

n-propyl

hydrogen

tert-butyl

n-propyl

hydrogen

iso-propyl

methyl

iso-butyl

methyl

tert-butyl

methyl

iso-propyl

ethyl

iso-butyl

ethyl

tert-butyl

ethyl

iso-propyl

ethyl

propyl

iso-butyl

ethyl

propyl

tert-butyl

ethyl

propyl

Tolyl

hydrogen

Xylyl

hydrogen

pyridyl

hydrogen

methylpyridyl

hydrogen

pyrimidyl

hydrogen

pyrazinyl

hydrogen

carbazolyl

hydrogen

dibenzofuranyl

hydrogen

dimethylfluorenyl

hydrogen

methylindonyl

hydrogen

—CH 2 -tolyl

hydrogen

—CH 2 -xylyl

hydrogen

—CH 2 -pyridyl

hydrogen

—CH 2 -pyrazinyl

hydrogen

—CH 2 -methylpyridinyl

hydrogen

—CH 2 -dibenzofuranyl

hydrogen

—CMe 2 -iso-butyl

hydrogen

cyclopentyl

hydrogen

cyclohexyl

hydrogen

adamantyl

hydrogen

—CH 2 -adamantyl

hydrogen

SiMe 3

hydrogen

SiPh 3

hydrogen

phenyl

methyl

tolyl

methyl

xylyl

methyl

pyridyl

methyl

methylpyridyl

methyl

pyrimidyl

methyl

pyrazinyl

methyl

carbazolyl

methyl

dibenzofuranyl

methyl

dimethylfluorenyl

methyl

methylindonyl

methyl

—CH 2 -tolyl

methyl

—CH 2 -xylyl

methyl

—CH 2 -pyridyl

methyl

—CH 2 -pyrazinyl

methyl

—CH 2 -methylpyridinyl

methyl

—CH 2 -dibenzofuranyl

methyl

100

—CMe 2 -iso-butyl

methyl

101

cyclopentyl

methyl

102

cyclohexyl

methyl

103

CF 3

methyl

104

CF 2 CF 3

methyl

105

SiMe 3

methyl

106

SiPh 3

methyl

A 1 is CR 2 or N;

A 2 is CR 3 or N;

A 3 is CR 4 or N;

A 4 is CR 5 or N;

A 1′ is CR 2′ or N;

A 2′ is CR 3′ or N;

A 3′ is CR 4′ or N;

A 4′ is CR 5′ or N;

R 2 , R 3 , R 4 , R 5 , R 2′ , R 3′ , R 4′ and R 5′

are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atom; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action;

R 2 and R 3 , R 3 and R 4 or R 4 and R 5 or R 2′ and R 3′ , R 3′ and R 4′ or R 4′ and R 5′ may form, independently of each other, together with the carbon atoms to which they are bonded, a saturated or unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, selected from O, S and N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 5 to 18 carbon atoms and/or heteroatoms; and

˜ in Formula (I) and Formula (I′) is the bonding site to the metal.

2. The organic electronic device according to claim 1 , wherein the organic electronic device is selected from organic light-emitting diodes (OLED), light-emitting electrochemical cells (LEEC), organic photovoltaic cells (OPV) and organic field-effect transistors (OFET).

3. The organic electronic device according to claim 1 , wherein the metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) is employed as emitter material in OLEDs or a LEECs or absorption dye in OPVs.

4. The organic electronic device according to claim 3 , wherein the OLED comprises

(a) an anode,

(b) a cathode,

wherein the metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) is present in the light-emitting layer of the OLED.

5. The organic electronic device according to claim 1 , wherein the groups A 1 , A 2 , A 3 , A 4 , A 1′ , A 2′ , A 3′ , and A 4′ , in the ligands of formulae (I) and (I′) have the following meanings:

A 1 is CR 2 or N;

A 2 is CR 3 or N;

A 3 is CR 4 or N;

A 4 is CR 5 or N;

A 1′ is CR 2′ or N;

A 2′ is CR 3′ or N;

A 3′ is CR 4′ or N;

A 4′ is CR 5′ or N;

R 2 , R 3 , R 4 , R 5 , R 2′ , R 3′ , R 4′ and R 5′

are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom[, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical, having a total of from 3 to 10 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 3 to 10 carbon atoms and/or heteroatoms; a group with donor or acceptor action, selected from halogen radicals, CF 3 , CN, SiPh 3 and SiMe 3 ; a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms.

6. The organic electronic device according to claim 1 , wherein the metal-carbene complex has one of the following formulae (II), (II′) or (II″)

wherein

M is Ir;

n is 1, 2 or 3;

L is a monoanionic bidentate ligand,

is 0, 1 or 2, where, when o=2, the L ligands may be the same or different;

n′ is 1 or 2;

n″ is 1 or 2; wherein the sum of n′+n″ is 2 or 3;

o′ is 0 or 1;

wherein the sum of n+o in formulae (II) and (II′) and the sum of n′+n″+o′ in formula (II″) is 3, with the proviso that n in formula (II) and (II′) is at least 1 and n′, as well as n″ formula (II″) are at least 1.

7. The organic electronic device according to claim 1 , wherein the metal-carbene complex has one of the following formulae (II), (II′) or (II″)

wherein

M is Pt;

n is 1 or 2;

L is a monoanionic bidentate ligand,

o is 0 or 1;

n′ is 1;

n″ is 1;

wherein the sum of n′+n″ is 2;

o′ is 0;

wherein the sum of n+o in formulae (II) and (II″) and the sum of n′+n″+o′ in formula (II″) is 2, with the proviso that n in formula (II) and (II″) is at least 1 and n′, as well as n″ in formula (II″) are both 1.

8. The organic electronic device according to claim 6 , wherein

n is 3;

n′ is 1 or 2,

n″ is 1 or 2,

wherein the sum of n′+n″ is 3.

9. The organic electronic device according to claim 6 , wherein the monoanionic bidentate ligand L in the metal-carbene complex has following meaning:

a ligand of formula (A)

in which

R 51 is in each case independently a linear or branched alkyl radical having 1 to 6 carbons atoms; a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms; a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms,

R 52 is hydrogen; a linear or branched alkyl radical having 1 to 6 carbon atoms; a substituted or unsubstituted aryl radical having 6 to 18 carbon atoms;

L is a carbene ligand of the general formula (B)

where

A 9′ is CR 12′ or N;

A 10′ is CR 13′ or N;

R 11′ is a linear or branched, substituted or unsubstituted alkyl radical having 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having 3 to 18 carbon atoms; a substituted or unsubstituted heterocycloalkyl radical interrupted by at least one heteroatom, selected from O, S and N, and having 3 to 18 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, selected from O, S and N and having a total of 5 to 30 carbon atoms and/or heteroatoms;

R 12′ , R 13′ are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having 3 to 18 carbon atoms; a substituted or unsubstituted heterocycloalkyl radical interrupted by at least one heteroatom, selected from O, S and N, and having 3 to 18 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, selected from O, S and N and having a total of 5 to 30 carbon atoms and/or heteroatoms; or a group with donor or acceptor action;

if A 9′ is CR 12′ and A 10′ is CR 13′ , CR 12′ and CR 12′ together may form, a saturated or unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, selected from O, S and N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 5 to 18 carbon atoms and/or heteroatoms;

A 5′ is CR 14′ or N;

A 6′ is CR 15′ or N;

A 7′ is CR 16′ or N;

A 8′ is CR 17′ or N;

R 14′ , R 15′ ,

R 16′ , R 17′ are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having 3 to 18 carbon atoms; a substituted or unsubstituted heterocycloalkyl radical interrupted by at least one heteroatom, selected from O, S and N, and having 3 to 18 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, selected from O, S and N and having a total of 5 to 30 carbon atoms and/or heteroatoms; or a group with donor or acceptor action;

R 14′ , and R 15′ , R 15′ , and R 16′ or R 16′ and R 17′ may form, together with the carbon atoms to which they are bonded, a saturated or unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, selected from O, S and N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 5 to 18 carbon atoms and/or heteroatoms;

if A 9′ is CR 12′ , R 12′ and R 17′ together may form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, selected from O, S and N, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms, and which are optionally substituted with aromatic units, heteroaromatic units or groups with donor or acceptor action;

q′ is 0 or 1;

L is a ligand of the general formula (C)

in which the symbols are each defined as follows:

D are each independently CR 34′″ or N;

W is C or N;

E are each independently CR 35′″ , N, NR 36′″ or O;

I is 1 or 2;

R 34′″ , R 35′″ , R 36′″

are each independently hydrogen; substituted or unsubstituted or branched alkyl; substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl;

in each case two R 34′″ , R 35′″ or R 35′″ radicals together form a fused ring which may optionally comprise at least one heteroatom;

R 34′″ , R 35′″ , R 36′″ or R 37′″ is a radical having donor or acceptor action;

where the dotted line means an optional bridge between one of the D groups and one of the E groups; where the bridge may be defined as follows:

alkylene, arylene, heteroarylene, alkynylene, alkenylene, NR 38′″ , O, S, SiR 41′″ R 42′″ , and (CR 43′″ R 44′″ ) v , where one or more nonadjacent (CR 43′″ R 44′″ ) groups may be replaced by NR 38′″ , O, S, SiR 41′″ R 42′″ , where

v is from 2 to 10;

and

R 38′″ , R 41′″ , R 42′″ , R 43′″ , R 44′″

are each H, alkyl, aryl or heteroaryl.

10. The organic electronic device according to claim 1 , wherein the metal-carbene complex is employed in combination with at least one host material.

11. A light-emitting layer comprising at least one metal-carbene complex as defined in claim 1 as emitter material.

12. An OLED comprising the metal-carbene complex as defined in claim 1 .

13. An apparatus selected from the group consisting of stationary visual display units, such as visual display units of computers, televisions, visual display units in printers, kitchen appliances, advertising panels, information panels and illuminations; mobile visual display units such as visual display units in smartphones, cellphones, tablet computers, laptops, digital cameras, MP3-players, vehicles, keyboards and destination displays on buses and trains; illumination units; units in items of clothing; units in handbags, units in accessories, units in furniture and units in wallpaper, comprising the organic electronic device of claim 1 .

14. A metal-carbene complex, wherein the metal is Ir or Pt, comprising one, two or three bidentate ligands of formula (I) and/or (I′)

wherein R 1 has the following meaning:

wherein:

m is 1;

˜ is the bonding site to the ligand of formula (I) or (I′); and

the group R 1 has one of the following definitions:

R 6

R 7

R 8

iso-butyl

methyl

hydrogen

tert-butyl

methyl

hydrogen

iso-butyl

ethyl

hydrogen

tert-butyl

ethyl

hydrogen

iso-propyl

n-propyl

hydrogen

iso-butyl

n-propyl

hydrogen

tert-butyl

n-propyl

hydrogen

iso-propyl

methyl

iso-butyl

methyl

tert-butyl

methyl

iso-propyl

ethyl

iso-butyl

ethyl

tert-butyl

ethyl

iso-propyl

ethyl

propyl

iso-butyl

ethyl

propyl

tert-butyl

ethyl

propyl

Tolyl

hydrogen

Xylyl

hydrogen

pyridyl

hydrogen

methylpyridyl

hydrogen

pyrimidyl

hydrogen

pyrazinyl

hydrogen

carbazolyl

hydrogen

dibenzofuranyl

hydrogen

dimethylfluorenyl

hydrogen

methylindonyl

hydrogen

—CH 2 -tolyl

hydrogen

—CH 2 -xylyl

hydrogen

—CH 2 -pyridyl

hydrogen

—CH 2 -pyrazinyl

hydrogen

—CH 2 -methylpyridinyl

hydrogen

—CH 2 -dibenzofuranyl

hydrogen

—CMe 2 -iso-butyl

hydrogen

cyclopentyl

hydrogen

cyclohexyl

hydrogen

adamantyl

hydrogen

—CH 2 -adamantyl

hydrogen

SiMe 3

hydrogen

SiPh 3

hydrogen

phenyl

methyl

tolyl

methyl

xylyl

methyl

pyridyl

methyl

methylpyridyl

methyl

pyrimidyl

methyl

pyrazinyl

methyl

carbazolyl

methyl

dibenzofuranyl

methyl

dimethylfluorenyl

methyl

methylindonyl

methyl

—CH 2 -tolyl

methyl

—CH 2 -xylyl

methyl

—CH 2 -pyridyl

methyl

—CH 2 -pyrazinyl

methyl

—CH 2 -methylpyridinyl

methyl

—CH 2 -dibenzofuranyl

methyl

100

—CMe 2 -iso-butyl

methyl

101

cyclopentyl

methyl

102

cyclohexyl

methyl

103

CF 3

methyl

104

CF 2 CF 3

methyl

105

SiMe 3

methyl

106

SiPh 3

methyl

A 1 is CR 2 or N;

A 2 is CR 3 or N;

A 3 is CR 4 or N;

A 4 is CR 5 or N;

A 1′ is CR 2′ or N;

A 2′ is CR 3′ or N;

A 3′ is CR 4′ or N;

A 4′ is CR 5′ or N;

R 2 , R 3 , R 4 , R 5 , R 2′ , R 3′ , R 4′ and R 5′

˜ is the bonding site to the metal.

15. A process for preparing a metal carbene complex according to claim 14 , by contacting suitable compounds comprising Ir or Pt with appropriate ligands or ligand precursors, wherein the ligand precursors are reacted with the suitable Ir or Pt comprising compounds and the carbene can be released from precursors of the carbene ligands by removing lower alcohols,

wherein the ligand precursor used is a compound of the general formula (IV)

wherein R 1 , A 1 , A 2 , A 3 , A 4 , A 1′ , A 2′ , A 3′ and A 4′ are each as defined in claim 14 , and

R 12 is independently SiR 13 R 14 R 15 , aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl,

R 3 , R 4 ,

R 15 are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.

16. The metal carbene complex according to claim 14 , wherein the group R 1 has one of the following definitions:

R 6

R 7

R 8

Tolyl

hydrogen

Xylyl

hydrogen

pyridyl

hydrogen

methylpyridyl

hydrogen

pyrimidyl

hydrogen

pyrazinyl

hydrogen

carbazolyl

hydrogen

dibenzofuranyl

hydrogen

dimethylfluorenyl

hydrogen

methylindonyl

hydrogen

—CH 2 -tolyl

hydrogen

—CH 2 -xylyl

hydrogen

—CH 2 -pyridyl

hydrogen

—CH 2 -pyrazinyl

hydrogen

—CH 2 -methylpyridinyl

hydrogen

—CH 2 -dibenzofuranyl

hydrogen

—CMe 2 -iso-butyl

hydrogen

cyclopentyl

hydrogen

cyclohexyl

hydrogen

adamantyl

hydrogen

—CH 2 -adamantyl

hydrogen

SiMe 3

hydrogen

SiPh 3

hydrogen

phenyl

methyl

tolyl

methyl

xylyl

methyl

pyridyl

methyl

methylpyridyl

methyl

pyrimidyl

methyl

pyrazinyl

methyl

carbazolyl

methyl

dibenzofuranyl

methyl

dimethylfluorenyl

methyl

methylindonyl

methyl

—CH 2 -tolyl

methyl

—CH 2 -xylyl

methyl

—CH 2 -pyridyl

methyl

—CH 2 -pyrazinyl

methyl

—CH 2 -methylpyridinyl

methyl

—CH 2 -dibenzofuranyl

methyl

—CMe 2 -methyl

methyl

—CMe 2 -ethyl

methyl

—CMe 2 -propyl

methyl

100

—CMe 2 -iso-butyl

methyl

101

cyclopentyl

methyl

102

cyclohexyl

methyl

methyl.

Priority Claims (1)

EP 13174779 · Jul 2, 2013 · regional

Continuity (2)

Continuation 14901738

Related Publication 20200251667A1 · Aug 6, 2020