Metal-assisted delayed fluorescent emitters containing tridentate ligands
Tridentate platinum, palladium, and gold complexes of Formulas A-I and A-II and tridentate iridium and rhodium compounds of Formulas B-I, B-II, and B-III suitable for delayed fluorescent and phosphorescent or phosphorescent emitters in display and lighting applications.
1. A compound represented by Formula B-I
wherein:
M is Ir or Rh,
each of L 1 and L 4 is independently a five-membered heterocyclyl with one, two, or three nitrogen atoms,
each of L 2 and L 5 is independently substituted or unsubstituted phenyl,
each of L 3 and L 6 is independently substituted or unsubstituted pyridine,
each of LP 1 , LP 2 , LP 3 , LP 4 , LP 5 , and LP 6 is independently a fluorescent luminophore, each of LP 1 , LP 2 , LP 3 , LP 4 , LP 5 , and LP 6 is independently present or absent, and at least one of LP 1 , LP 2 , LP 3 , LP 4 , LP 5 , and LP 6 is present,
A 1 and A 2 are each independently NH, NR 3 , or O, and A 1 optionally forms more than one bond with L 2 , L 3 , or both, thereby forming a ring system with L 2 , a ring system with L 3 , or both, and A 2 optionally forms more than one bond with L 5 , L 6 , or both, thereby forming a ring system with L 5 , a ring system with L 6 , or both,
each of V 1 , V 3 , V 4 , and V 6 is independently N or C,
each of V 2 and V 5 is C,
each of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , and Y 8 is independently C, N, O, or S,
each of R a , R b , R c , R d , R e , and R f is independently present or absent, and if present each of R a , R b , R c , R d , R e , and R f is independently a mono-, di-, tri- or tetra substitution, and each R a , R b , R c , R d , R e , and R f is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof, and
R 3 is hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
2. The compound of claim 1 , wherein the compound is represented by one of Formulas B-1 to B-5:
wherein Formulas B-1 through B-5 are symmetrical, and for Formulas B-1 through B-5:
L 2 is substituted or unsubstituted phenyl,
L 3 is substituted or unsubstituted pyridine,
each of LP 1 , LP 2 , and LP 3 is independently a fluorescent luminophore, each of LP 1 , LP 2 , and LP 3 is independently present or absent, and at least one of LP 1 , LP 2 , and LP 3 is present,
A is NH, NR 3 , or O,
each of V 1 and V 3 is independently N or C,
V 2 is C,
each of Y 1 , Y 2 , Y 3 , and Y 4 is independently C, N, O, or S,
each of R a , R b , and R c is independently present or absent, and if present each of R a , R b , and R c is independently a mono-, di-, or tri-substitution, and each R a , R b , and R c is independently deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof,
R 3 is hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof,
X is N,
each of Z is a linking atom or linking group, and
R x is present or absent, and if present each R x is a mono-, di-, tri-, or tetra-substitution, and
each R x is independently deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
3. The compound of claim 2 , wherein each of LP 1 , LP 2 , and LP 3 , if present, is independently selected from the group consisting of:
an aromatic hydrocarbon, an aromatic hydrocarbon derivative, a polyphenyl hydrocarbon, a hydrocarbon with condensed aromatic nuclei, naphthalene, anthracene, phenanthrene, chrysene, pyrene, triphenylene, perylene, acenaphthene, tetracene, pentacene, tetraphene, coronene, fluorene, biphenyl, p-terphenyl, o-diphenylbenzene, m-diphenylbenzene, p-quaterphenyl, benzo[a]tetracene, benzo[k]tetraphene, indeno[1,2,3-cd]fluoranthene, tetrabenzo[de,hi,op,st]pentacene, an arylethylene derivative, an arylacetylene derivative, a diarylethylene, a diarylpolyene, a diaryl-substituted vinylbenzene, a distyrylbenzene, a trivinylbenzene, an arylacetylene, a functional substitution product of stilbene, a five-, six- or seven-membered heterocyclic compound derivative, a furan derivative, a thiophene derivative, a pyrrole derivative, an aryl-substituted oxazole, an 1,3,4-oxadiazole, an 1,3,4-thiadiazole, an aryl-substituted 2-pyrazoline, an aryl-substituted pyrazole, a benzazole, 2H-benzotriazole, a substitution product of 2H-benzotriazole, a heterocycle with one, two, or three nitrogen atoms, an oxygen-containing heterocycle, a coumarin, a coumarin derivative, a dye, an acridine dye, a xanthene dye, an oxazine, thiazine, and derivatives thereof.
4. The compound of claim 2 , wherein
is one of the following:
wherein:
n is an integer from 0 to 4,
m is an integer from 1 to 3,
each of R s , R t , R u , and R v is hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, and any conjugate or combination thereof.
5. The compound of claim 1 , wherein each of
is independently selected from the group consisting of:
6. The compound of claim 1 , wherein:
each of
independently represents one of the following structures:
each of
independently represents one of the following structures:
and
each of
independently represents one of the following structures:
and
R is hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, deuterium, halogen, hydroxyl, thiol, nitro, cyano, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramide, mercapto, sulfo, carboxyl, hydrazino, substituted silyl, polymeric, or any conjugate or combination thereof.
7. The compound of claim 2 , wherein each of LP 1 , LP 2 , and LP 3 , if present, is independently selected from the group consisting of:
aromatic hydrocarbons selected from the group consisting of:
and derivatives thereof,
arylethylenes and arylacetylenes selected from the group consisting of:
and derivatives thereof,
heterocyclic compounds selected from the group consisting of:
and derivatives thereof, and
other fluorescent luminophores selected from the group consisting of:
wherein:
each of R al , R bl , R cl , R dl , R el , R fl , R gl , R hl , and R i1 independently represents one of the following structures:
each of R 1l , R 2l , R 3l , R 4l , R 5l , R 6l , R 7l and R 8l is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof,
each of Y a , Y b , Y c , Y d , Y e , Y f , Y g , Y h , Y i , Y j , Y k , Y l , Y m , Y n , Y o and Y p is independently C, N, or B,
each of U a , U b and U 2 is independently CH 2 , CR 1 R 2 , C═O, CH 2 , SiR 1 R 2 , GeH 2 , GeR 1 R 2 , NH, NR 3 , PH, PR 3 , R 3 P═O, AsR 3 , R 3 As═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BH, BR 3 , R 3 Bi═O, BiH, or BiR 3 , and
each of W a , W b , and W is independently CH, CLR 1 , SiR 1 , GeH, GeR 1 , N, P, B, Bi, or Bi═O.
8. A device comprising the compound of claim 2 , wherein the device is an organic light emitting diode or a full color display.
9. The compound of claim 1 , wherein the compound is represented by one of Formulas B-11 through B-25
wherein Formulas B-11 through B-25 are asymmetrical, and for Formulas B-11 through B-25:
A is independently NH, NR 3 , or O,
each of X, X 1 , and X 2 is independently N,
each of Z, Z 1 , and Z 2 is a linking atom or linking group, and
each of R x and R y is independently present or absent, and if present each of R x and R y is a mono-, di-, tri-, or tetra-substitution, and each R x and R y is independently deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof.
10. The compound of claim 9 , wherein each of LP 1 , LP 2 , LP 3 , LP 4 , LP 5 and LP 6 , if present, is independently selected from the group consisting of:
an aromatic hydrocarbon, an aromatic hydrocarbon derivative, a polyphenyl hydrocarbon, a hydrocarbon with condensed aromatic nuclei, naphthalene, anthracene, phenanthrene, chrysene, pyrene, triphenylene, perylene, acenaphthene, tetracene, pentacene, tetraphene, coronene, fluorene, biphenyl, p-terphenyl, o-diphenylbenzene, m-diphenylbenzene, p-quaterphenyl, benzo[a]tetracene, benzo[k]tetraphene, indeno[1,2,3-cd]fluoranthene, tetrabenzo[de,hi,op,st]pentacene, an arylethylene derivative, an arylacetylene derivative, a diarylethylene, a diarylpolyene, a diaryl-substituted vinylbenzene, a distyrylbenzene, a trivinylbenzene, an arylacetylene, a functional substitution product of stilbene, a five-, six- or seven-membered heterocyclic compound derivative, a furan derivative, a thiophene derivative, a pyrrole derivative, an aryl-substituted oxazole, an 1,3,4-oxadiazole, an 1,3,4-thiadiazole, an aryl-substituted 2-pyrazoline, an aryl-substituted pyrazole, a benzazole, 2H-benzotriazole, a substitution product of 2H-benzotriazole, a heterocycle with one, two, or three nitrogen atoms, an oxygen-containing heterocycle, a coumarin, a coumarin derivative, a dye, an acridine dye, a xanthene dye, an oxazine, thiazine, and derivatives thereof.
11. The compound of claim 9 , wherein each of
and
is independently one of the following:
wherein:
n is an integer from 0 to 4,
m is an integer from 1 to 3,
each of R s , R t , R u , and R v is hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, and any conjugate or combination thereof.
12. The compound of claim 9 , wherein each of
is independently selected from the group consisting of:
13. The compound of claim 9 , wherein:
each of
independently represents one of the following structures:
each of
independently represents one of the following structures:
and
each of
independently represents one of the following structures:
and
R is hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, deuterium, halogen, hydroxyl, thiol, nitro, cyano, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramide, mercapto, sulfo, carboxyl, hydrazino, substituted silyl, polymeric, or any conjugate or combination thereof.
14. The compound of claim 9 , wherein each of LP 1 , LP 2 , LP 3 , LP 4 , LP 5 and LP 6 , if present, is independently selected from the group consisting of:
aromatic hydrocarbons selected from the group consisting of:
and derivatives thereof,
arylethylenes and arylacetylenes selected from the group consisting of:
and derivatives thereof,
heterocyclic compounds selected from the group consisting of:
and derivatives thereof, and
other fluorescent luminophores selected from the group consisting of:
wherein:
wherein R al , R bl , R cl , R dl , R cl , R dl , R el , R fl , R gl , R hl and R jl independently represents one of the following structures:
each of R 1l , R 2l , R 3l , R 4l , R 5l , R 6l , R 7l and R 8l is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof,
each of Y a , Y b , Y c , Y d , Y e , Y f , Y g , Y h , Y i , Y j , Y k , Y l , Y m , Y n , Y o and Y p is independently C, N, or B,
each of U a , U b and U 2 is independently CH 2 , CR 1 R 2 , C═O, CH 2 , SiR 1 R 2 , GeH 2 , GeR 1 R 2 , NH, NR 3 , PH, PR 3 , R 3 P═O, AsR 3 , R 3 As═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BH, BR 3 , R 3 Bi═O, BiH, or BiR 3 , and
each of W a , W b , and W is independently CH, CLR 1 , SiR 1 , GeH, GeR 1 , N, P, B, Bi, or Bi═O.
15. A device comprising the compound of claim 9 , wherein the device is an organic light emitting diode or a full color display.