Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues

1. A complex of Formula AI:

wherein:

M is Pt or Pd,

V 1 is coordinated with M and is N,

V 2 is coordinated with M and is C,

V 3 is coordinated with M and is C,

V 4 is coordinated with M and is N or C,

each of L 2 and L 3 is independently substituted or unsubstituted aryl,

L 1 and V 1 combine to form a substituted or unsubstituted six membered heteroaryl,

L 4 and V 4 combine to form a substituted or unsubstituted five membered to ten membered heteroaryl having at least one heteroatom;

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

A 4 is a single bond or O,

X 1 is 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, and

each of R x 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.

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

3. The complex of claim 1 , wherein the complex is represented by one of the chemical structures in Structure 1-Structure 6

wherein each of R 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.

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. The complex of claim 1 , wherein

is one of the following structures:

6. The complex of claim 1 , wherein

is one of 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.

7. The complex of claim 1 , wherein each of

is independently one of the following structures:

8. An emitter comprising the complex of claim 3 .

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

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

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

12. A device comprising a complex of claim 1 .

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