Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues

1. A complex of Formula AIV:

wherein:

M is Pt or Pd,

V 1 and V 4 are N,

V 2 and V 3 are C,

L 1 and L 4 are pyridyl;

L 2 and L 3 are phenyl;

each of A 1 , A 2 , A 3 , and A 4 is independently a single bond, CR 1 R 2 , C═O, SiR 1 R 2 , GeR 1 R 2 , NR 3 , PR 3 , R 3 P═O, AsR 3 , R 3 As═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BR 3 , R 3 Bi═O, or BiR 3 ,

A 5 is O, NR 3 , CR 1 R 2 , or C═O,

X 1 and X 2 are N,

each of R a , R b , R c , and R d is independently present or absent, and if present each of R a , R b , R c , and R d is independently a mono-, di-, or tri-substitution as valency permits, and each of R a , R b , R c , and R d 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 R x and R y 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, 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, 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 le and le are optionally linked together.

2. The complex of claim 1 , wherein the complex has a neutral charge.

3. A complex represented by one of the chemical structures:

wherein M is Pt or Pd, and

each of R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 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.

4. The complex of claim 1 , wherein each of

is independently one of the following structures:

wherein each of 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.

5. An emitter comprising the complex of claim 3 .

6. An emitter comprising the complex of claim 1 , wherein the emitter is a delayed fluorescent and phosphorescent emitter.

7. An emitter comprising the complex of claim 1 , wherein the emitter is a phosphorescent emitter.

8. An emitter comprising the complex of claim 1 , wherein the emitter is a delayed fluorescent emitter.

9. The complex of claim 1 , wherein polymeric comprises polyalkylene, polyester, or polyether.

10. The complex of claim 9 , wherein polymeric comprises —(CH 2 O) n —CH 3 , —(CH 2 CH 2 O) n —CH 3 , —[CH 2 CH(CH 3 )] n —CH 3 , —[CH 2 CH(COOCH 3 )] n —CH 3 , —[CH 2 CH(COOCH 2 CH 3 )] n —CH 3 , or —[CH 2 CH(COO t Bu)] n —CH 3 , where n is an integer.

11. A device comprising a complex of claim 1 .

12. The complex of claim 1 , wherein each of A 1 , A 2 , A 3 , and A 4 is independently a single bond, CR 1 R 2 , C═O, SiR 1 R 2 , NR 3 , O, S, S═O, or SO 2 .

13. The complex of claim 1 , wherein each of A 1 , A 2 , A 3 , and A 4 is independently a single bond, CR 1 R 2 , NR 3 , or O.

14. The complex of claim 1 , wherein each of A 1 , A 2 , A 3 , and A 4 is independently a single bond or CR 1 R 2 .

15. The complex of claim 1 , wherein A 5 is O, NR 3 , or CR 1 R 2 .

16. The complex of claim 1 , wherein A 5 is O.

17. The complex of claim 1 , wherein each R 1 , R 2 and R 3 is independently hydrogen, deuterium, halogen, hydroxyl; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, alkoxy, aryloxy, or haloalkyl.

18. The complex of claim 1 , wherein each R 1 , R 2 and R 3 is independently hydrogen; substituted or unsubstituted: aryl, alkyl, alkenyl, or alkynyl.

19. The complex of claim 1 , wherein each of R a , R b , R c , and R d is independently present or absent, and if present each of R a , R b , R c , and R d is independently a mono-, di-, or tri-substitution as valency permits, and each of R a , R b , R c , and R d is independently hydrogen, halogen, hydroxyl; substituted or unsubstituted: aryl, heteroaryl, alkyl, alkenyl, or alkynyl, and

each of R x and R y is independently hydrogen, halogen, hydroxyl; substituted or unsubstituted: aryl, heteroaryl, alkyl, alkenyl, or alkynyl.

20. The complex of claim 1 , wherein the complex is