Tetradentate platinum and palladium complex emitters containing phenyl-pyrazole and its analogues

1. A compound of Formula I, Formula A-2, or Formula A-3:

wherein M is platinum or palladium,

wherein L 1 is selected from the following structures:

wherein Y 1 is O, N, or S; Y 2 is N or C; Y 3 is N or C, Y 4 is N; and V 1 is a carbene carbon;

wherein L 2 and L 3 each represent phenylene;

wherein L 4 is substituted or unsubstituted pyridine;

wherein each of F 1 and F 2 is independently present or absent, wherein at least one of F 1 and F 2 is present, and each of F 1 and F 2 present is a fluorescent luminophore,

wherein each of A 1 , A 2 , and A is independently NR 3 or O,

wherein V 2 is C; V 3 is C; and V 4 is N;

wherein each of X is N,

wherein R a is present or absent, wherein R b is present or absent, wherein R c is present or absent, wherein R d is present or absent, wherein Rx is present or absent, and if present each of Rx, R a , R b , R c , and R d independently represents mono-, di-, or tri-substitutions, and wherein each of R x , R a , R b , R c , and R d 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

wherein each R 3 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, monarylamino, 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 each of F 1 and F 2 present is independently selected from aromatic hydrocarbons and their derivatives, polyphenyl hydrocarbons, hydrocarbons with condensed aromatic nuclei, naphthalene, anthracene, phenanthrene, chrysene, pyrene, triphenylene, perylene, acenapthene, 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 and their derivatives, diarylethylenes, diarylpolyenes, diaryl-substituted vinylbenzenes, distyrylbenzenes, trivinylbenzenes, arylacetylenes, and functional substitution products of stilbene.

3. The compound of claim 1 , wherein each of F 1 and F 2 , if present, is independently selected from substituted or unsubstituted five-, six- or seven-membered heterocyclic compounds, furan, thiophene, pyrrole and their derivatives, aryl-substituted oxazoles, 1,3,4-oxadiazoles, 1,3,4-thiadiazoles, aryl-substrtuted 2-pyrazolines and pyrazoles, bnezazoles, 2H-benzotriazole and its substitution products, heterocycles with one, two or three nitrogen atoms, oxygen-containing heterocycles, coumarins and their derivatives, miscellaneous dyes, acridine dyes, xanthene dyes, oxazines, and thiazines.

4. The compound of claim 1 , wherein the compound has the structure of Formula III, or Formula V:

wherein each of 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.

5. The compound of claim 1 , wherein the compound has the structure of Formula VII:

wherein, if F 1 is present, R e and R f are on the ortho-positions of the bond between F 1 and L 1 , wherein, if F 2 is present, R g and R h are on the ortho-positions of the bond between F 2 and L 2 ,

wherein each of R e , R f , R g , R h , if present, 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.

6. The compound of claim 1 , wherein the compound has the structure of Formula A-1, Formula A-2, or Formula A-3:

wherein each of X is N,

wherein R x is present or absent, and if present each of R x independently represents mono-, di-, or tri-substitutions, and wherein each of Rx present 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.

7. The compound of claim 1 , wherein the compound has a neutral charge.

8. The compound of claim 1 , wherein

is selected from the following structures:

wherein R 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.

9. The compound of claim 1 , wherein each of

is the following structure:

10. The compound of claim 1 , wherein each of F 1 and F 2 , if present, is independently selected from the following structures:

wherein each of R 11 , R 21 , R 31 , R 41 , R 51 , R 61 , R 71 , R 81 , R 91 , and R 101 is independently a mono-, di-, or tri-substitution, and each of R 11 , R 21 , R 31 , R 41 , R 51 , R 61 , R 71 and R 81 , if present, 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,

wherein 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 , if present, is independently C, N or B,

wherein each of U a and U b if present, 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

wherein each of W a , W b and W, if present, is independently are CH, CR 1 , SiR 1 , GeH, GeR 1 , N, P, B, Bi, or Bi═O.

11. The compound of claim 1 , wherein F 1 , if present, is covalently bonded to L 1 directly, or F 2 , if present, is covalently bonded to L 2 directly, or a combination thereof.

12. An emitter comprising the compound of claim 1 , wherein the emitter is a delayed fluorescent or a phosphorescent emitter.

13. A compound represented by one of follow structures:

wherein each of R 1 , R 2 , and 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, dialkylamino, monarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof;

wherein M is Pt or Pd.

14. An emitter comprising the compound of claim 13 , wherein the emitter is a delayed fluorescent emitter or a phosphorescent emitter.

15. A light-emitting device comprising a compound of claim 1 .