Metal-assisted delayed fluorescent emitters containing tridentate ligands

1. A compound represented by Formula A-1:

wherein:

M is Pt, Pd, or Au,

L 1 is a five-membered heterocyclyl, five-membered heteroaryl, five-membered carbene, or five-membered N-heterocyclic carbene,

L 2 is phenyl,

L 3 is pyridyl,

R L4 is an inorganic anion or organic anion,

each of LP 1 , LP 2 , and LP 3 is independently present or absent, wherein at least one of LP 1 , LP 2 , or LP 3 is present and is independently 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, arylethylene, arylacetylene, 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, a 1,3,4-oxadiazole, a 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, a thiazine, or a derivative thereof,

A is O,

V 1 is N, C, P, B, or Si,

V 2 is C,

V 3 is N,

each of Y 1 , Y 2 , Y 3 , and Y 4 is independently C, N, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , PR 3 , R 3 P═O, AsR 3 , R 3 As═O, or BR 3 ,

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-, tri-, or tetra-substitution, valency permitting, 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, and

each of R 3 is independently 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, or polymeric; or any conjugate or combination thereof.

2. The compound of claim 1 , wherein M-R L4 is one of:

wherein each of R p , R q , and R r 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, di alkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, and polymeric; or any conjugate or combination thereof.

3. The compound of claim 1 , wherein the five-membered heterocyclyl

represents one of the following structures:

4. The compound of claim 1 , wherein:

represents one of the following structures:

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.

5. The compound of claim 1 , wherein each of LP 1 , LP 2 and LP 3 , if present, independently represents one of the following structures:

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 il independently represents one of the following structures:

each R 1l , R 2l , R 3l , R 4l , R 5l , R 6l , R 7l , R 8l , R 9l and R 10l 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 ,

each of W, W a , and W b is independently CH, CR 1 , SiR 1 , GeH, GeR 1 , N, P, B, Bi, and Bi═O, and

each of R 1 , R 2 , R 3 and R 4 is independently 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, or polymeric; or any conjugate or combination thereof.

6. The compound of claim 1 , wherein each LP 1 , LP 2 and LP 3 , if present, is independently bonded indirectly to L 1 , L 2 , or L 3 , respectively, through a linking atom or linking group selected from the group consisting of:

wherein:

x is an integer from 1 to 10,

each of R t , Rv, R sl , R tl , R ul , and R vl 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, di alkylamino, 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, and

wherein the linking atom or linking group is covalently bonded to any atom of LP 1 , LP 2 , and LP 3 as valency permits.

7. The compound of claim 1 , wherein M is Pt.

8. The compound of claim 1 , wherein L 1 is a five-membered heterocyclyl, five-membered heteroaryl, five-membered carbene, or five-membered N-heterocyclic carbene.

9. The compound of claim 1 , wherein L 1 is a five-membered heterocyclyl or five-membered heteroaryl.

10. The compound of claim 1 , wherein L 1 is pyrazolyl or imidazolyl.

11. The compound of claim 1 , wherein LP 1 is present, and LP 2 and LP 3 are absent.

12. The compound of claim 1 , wherein LP 1 is present and is 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, or tetrabenzo[de,hi,op,st]pentacene.

13. The compound of claim 1 , wherein LP 1 is present and is an aromatic hydrocarbon.

14. The compound of claim 5 , wherein LP 1 is present and is

15. The compound of claim 1 , wherein V 1 is independently N or C.

16. The compound of claim 1 , wherein each of Y 1 , Y 2 , Y 3 , and Y 4 is independently C or N.

17. The compound of claim 1 , wherein the compound is selected from:

18. The compound of claim 1 , wherein the compound is a delayed fluorescent and phosphorescent emitter, a phosphorescent emitter, or a delayed fluorescent emitter.

19. A device comprising the compound of claim 1 , wherein the device is an organic light emitting diode or a full color display.

20. The compound of claim 1 , wherein the compound is selected from:

wherein:

each of R, R 1 , and R 2 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, di alkylamino, 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.