Tetradentate platinum and palladium complex emitters containing phenyl-pyrazole and its analogues
A phosphorescent emitter or delayed fluorescent and phosphorescent emitters represented by Formula 1 or Formula II, where M is platinum or palladium.
1. A compound of Formula I:
wherein M is platinum or palladium,
L 1 is diazolyl,
each L 2 and L 3 is phenyl,
L 4 is pyridyl,
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 independently selected from the following structures:
1. Aromatic Hydrocarbons and their Derivatives
2. Arylethylene, Arylacetylene and their Derivatives
3. Heterocyclic Compounds and their Derivatives
4. Other Fluorescent Luminophors
each of R 1l , R 2l , R 3l , R 4l , R 5l , R 6l , R 7l , R 8l , R 9l and R 10l is independently a mono-, di-, or tri-substitution, and each of R 1l , R 2l , R 3l , R 4l , R 5l , R 6l , R 7l , R 8l , R 9l and R 10l , 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, 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,
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,
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 ,
each of W, W a , and W b , if present, is independently CH, CR 1 , SiR 1 , GeH, GeR 1 , N, P, B, Bi, or Bi═O,
A 1 is O,
A 2 is O, N, or NR 3 ,
each V 1 and V 4 is N;
each V 2 and V 3 is C,
each Y 1 , Y 2 , and Y 3 is C,
Y 4 is N,
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, and if present each of R a , R b , R c , and R d independently represents mono-, di-, or tri-substitutions, and wherein each of 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, or two R a , two R b , two R c , or two R d optionally combine together form a ring; and
each of R 1 , R 2 , and 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; wherein each pair of R 3 and R c , R 3 and R d , R 3 and L 3 , and R 3 and L 4 optionally combine together form a ring.
2. 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 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 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 , and 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.
4. The compound of claim 1 , wherein the compound has the structure of anyone of Formulas A1-A23:
wherein each A, A 1 , X and X 1 between ring L 2 and L 3 is O,
each A, A 2 , X, and X 2 between rings L 3 and L 4 is N or O,
wherein each Z, Z 1 , and Z 2 is independently a linking atom or group,
wherein R x is present or absent, wherein R y is present or absent, and if present each of R x and R y independently represents mono-, di- or tri-substitutions, and wherein each of R x and R y 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.
5. The compound of claim 1 , wherein the compound has a neutral charge.
6. The compound of claim 4 , wherein each of Z, Z 1 , and Z 2 is independently selected from the following:
wherein n is an integer from 0 to 4,
wherein m is an integer from 1 to 3,
wherein each of R, R 1 , R 2 , R 3 , and R 4 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.
7. The compound of claim 1 , wherein F 1 , if present, is covalently bonded to L 1 directly, F 2 , if present, is covalently bonded to L 2 directly, or a combination thereof.
8. The compound of claim 7 , wherein F 1 , if present, is covalently bonded to L 1 by a linking atom or linking group, F 2 , if present, is covalently bonded to L 2 by a linking atom or linking group.
9. The compound of claim 8 , wherein each linking atom or linking group is independently selected from the following:
wherein x is an integer from 1 to 10,
wherein each of R sl , R tl , R ul , and R vl , 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.
10. An emitter comprising the compound of claim 1 , wherein the emitter is a delayed fluorescent and phosphorescent emitter.
11. An emitter comprising the compound claim 1 , wherein the emitter is a phosphorescent emitter.
12. An emitter comprising the compound of claim 1 , wherein the emitter is a delayed fluorescent emitter.
13. A light-emitting device comprising a compound of claim 1 .
14. The light-emitting device of claim 13 , wherein the compound demonstrates 100% internal quantum efficiency in the device settings.
15. The light emitting device of claim 13 , wherein the device is an organic light emitting diode.
16. A compound represented by one of the following structures:
wherein:
M is platinum or palladium;
n is an integer; and
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, 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.
17. An emitter comprising the compound of claim 16 , wherein the emitter is a delayed fluorescent emitter.
18. A light-emitting device comprising a compound of claim 16 .
19. The light-emitting device of claim 18 , wherein the compound demonstrates 100% internal quantum efficiency in the device settings.
20. A compound represented by one of the following structures: