Method for producing halogen-crosslinked iridium dimer

Patent metadata

Field	Value
Publication number	US-10844086-B2
Application number	US-201716301172-A
Country	US
Kind code	B2
Filing date	Jun 16, 2017
Priority date	Jun 24, 2016
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

A method for producing a halogen-crosslinked iridium dimer with increased purity that is used as a precursor in production of a cyclometalated iridium complex useful as a phosphorescent material for organic electroluminescent devices, organic electrochemiluminescent devices, luminescent sensors, photosensitizing pigments, photocatalysts, luminescent probes, various light sources, and the like. The halogen-crosslinked iridium dimer is represented by the following formula:

In this formula, each X represents a halogen atom, each CyA represents an optionally substituted five- or six-membered cyclic ring containing nitrogen atoms, and is linked to iridium via the nitrogen atoms, and each CyB represents an optionally substituted five- or six-membered ring containing carbon atoms, and is linked to iridium via the carbon atoms. CyA and CyB can be linked together to form an optionally substituted ring.

First claim

The invention claimed is:

1. A method for producing a halogen-crosslinked iridium dimer represented by the Formula (3):

wherein:
each X represents a halogen atom; and
each

represents Formula (4), Formula (5), Formula (6), Formula (7), Formula (9), Formula (10), Formula (11), Formula (12), Formula (13), or Formula (14):

wherein:
R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 89 , R 90 , R 91 , R 92 , R 93 , and R 94 independently represent hydrogen, alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, heterocyclyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, ureido, phosphoramido, hydroxy, mercapto, halogen, cyano, sulfo, carboxy, nitro, trifluoromethyl, hydroxamic acid, sulfino, hydrazino, imino, heterocyclyl, trialkylsilyl, or trialkylsilyloxy;

the method comprising:
reacting an iridium compound represented by the Formula (1):

wherein:
R 1 represents hydrogen, alkyl, or aryl, wherein the alkyl or aryl is optionally substituted with one or more halogens;
R 2 represents hydrogen, alkyl, or aryl, wherein the alkyl or aryl is optionally substituted with one or more halogens;
R 3 represents hydrogen, alkyl, or aryl, wherein the alkyl or aryl is optionally substituted with one or more halogens;
R 4 represents hydrogen, alkyl, or aryl, wherein the alkyl or aryl is optionally substituted with one or more halogens;
R 5 represents hydrogen, alkyl, or aryl, wherein the alkyl or aryl is optionally substituted with one or more halogens;
R 6 represents hydrogen, alkyl, or aryl, wherein the alkyl or aryl is optionally substituted with one or more halogens;
each X represents a halogen atom; and
Y represents a counter cation selected from the group consisting of a proton, a sodium cation, a potassium cation, an ammonium cation, a phosphonium cation, a sulfonium cation, a pyrrolidinium cation, a piperidinium cation, an imidazolium cation, and a pyridinium cation;

with an aromatic bidentate ligand represented by the Formula (2):

wherein:
Formula (2) represents Formula (4), Formula (5), Formula (6), Formula (7), Formula (9), Formula (10), Formula (11), Formula (12), Formula (13), or Formula (14):

wherein:
R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 89 , R 90 , R 91 , R 92 , R 93 , and R 94 independently represent hydrogen, alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, heterocyclyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, ureido, phosphoramido, hydroxy, mercapto, halogen, cyano, sulfo, carboxy, nitro, trifluoromethyl, hydroxamic acid, sulfino, hydrazino, imino, heterocyclyl, trialkylsilyl, or trialkylsilyloxy;

in the presence of a solvent having a boiling point in the range of 50° C. to 350° C.;
wherein the reaction between the iridium compound represented by the Formula (1) and the aromatic bidentate ligand represented by the Formula (2) is performed under atmospheric pressure; and
wherein the molar ratio of the aromatic bidentate ligand represented by the Formula (2) to the iridium compound represented by the Formula (1) is in the range of 0.5 to 10.

2. The method according to claim 1 , wherein the aromatic bidentate ligand represented by the Formula (2) represents Formula (4), Formula (7), Formula (9), or Formula (10):

wherein:
R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , and R 61 independently represent hydrogen, alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, heterocyclyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, ureido, phosphoramido, hydroxy, mercapto, halogen, cyano, sulfo, carboxy, nitro, trifluoromethyl, hydroxamic acid, sulfino, hydrazino, imino, heterocyclyl, trialkylsilyl, or trialkylsilyloxy.

3. The method according to claim 1 , wherein the aromatic bidentate ligand represented by the Formula (2) represents Formula (11) or Formula (14):

wherein:
R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 86 , R 87 , R 88 , R 89 , R 90 , R 91 , R 92 , R 93 , and R 94 independently represent hydrogen, alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, heterocyclyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, ureido, phosphoramido, hydroxy, mercapto, halogen, cyano, sulfo, carboxy, nitro, trifluoromethyl, hydroxamic acid, sulfino, hydrazino, imino, heterocyclyl, trialkylsilyl, or trialkylsilyloxy.

Assignees

• Aist

Inventors

• Konno Hideo
• Taniuchi Junichi
• Kobayashi Rumi
• Masahiro Yasushi

Classifications

• C07F15/004 Primary

  without a metal-carbon linkage · CPC title

• C07F15/00

  Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table · CPC title

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title

• C09K11/06

  containing organic luminescent materials · CPC title

• C09K2211/1037

  with sulfur · CPC title