Tridentate cyclometalated metal complexes with six-membered coordination rings

1. A complex of formula:

wherein:

M is Pt(II), Pd(II), Ir(I), Rh(I), or Au(II);

A is O, S, NR, PR, AsR, CR 2 , SiR 2 , or BR;

Y is Cl, Br, I, OR, OCOR, SR, NRR, or C≡CR;

each R is independently hydrogen, halogen, or substituted or unsubstituted: alkyl, alkenyl, alkynyl, or aryl;

is:

each n is independently an integer of 1 to 4, valency permitting,

each R 1 and R 2 is independently hydrogen, halogen, hydroxyl, amino, nitro, thiol, or substituted or unsubstituted: alkyl, alkoxyl, alkenyl, alkynyl, heteroaryl, or aryl, and any two of R 1 , and any two of R 2 are optionally linked together.

2. The complex of claim 1 , wherein

is

3. A complex represented by Formula 2:

wherein:

M is Pt(II), Pd(II), Ir(I), Rh(I), or Au(II),

x=0 or 1, and when x=0, Y 3e is directly linked to Y 3b ;

y=0 or 1, and when y=0, Y 2a is directly linked to Y 4b ;

z=0 or 1, and when m=0, Y 2c is directly linked to Y 2d ;

each of Ar 1 , Ar 2 , and Ar 3 independently represents five-membered heteroaryl or six-membered aryl or heteroaryl,

each n is independently an integer of 1 to 4, valency permitting,

each R 1 , R 2 , R 3 , and R 5 is independently hydrogen, halogen, hydroxyl, amino, nitro, thiol, or substituted or unsubstituted: alkyl, alkoxyl, alkenyl, alkynyl, heteroaryl, or aryl, and any two of R 1 , any two of R 2 , any two of R 3 , and any two R 5 are optionally linked together,

Y 1a is O, S, NR 2a , C, CR 2a , CR 2b R 2c , PR 2a , AsR 2a , BR 2a , or SiR 2d R 2e , where each of R 2a , R 2b , R 2c , R 2d , and R 2e is independently hydrogen, halogen, or substituted or unsubstituted: alkyl, alkenyl, alkynyl, or aryl;

Y 1b is O, S, NR 3a , C, CR 3a , CR 3b R 3c , PR 2a , AsR 2a , BR 2a , P(O)R 2a , As(O)R 2a , or SiR 3d R 3e , where each of R 3a , R 3b , R 3c , R 3d , and R 3e is independently hydrogen, halogen, or substituted or unsubstituted: alkyl, alkenyl, alkynyl, or aryl,

each of Y 2a and Y 2d is independently C, N, NR 4a , or CR 4b , where each of R 4a and R 4b is independently hydrogen, hydroxyl, amino, nitro, thiol, or substituted or unsubstituted: C 1 -C 4 alkyl, alkoxy, or aryl;

each of Y 2b and Y 2c is independently C or N,

each of Y 3a , Y 3b , Y 3c , Y 3d and Y 3e is independently C, N, O, S, NR 5a , PR 5b , AsR 5e , SiR 5d R 5e , BR 5f , or CR 5g , where each of R 5a , R 5b , R 5c , R 5d , R 5e , R 5f , and R 5g is independently hydrogen or substituted or unsubstituted: C 1 -C 4 alkyl or aryl; or ZR 6a R 6b ; Z is C or Si; and each of R 6a and R 6b is independently substituted or unsubstituted C 1 -C 4 alkyl or aryl,

each of Y 4a , Y 4b , Y 4c , and Y 4d is independently N, NR 4e , C, or CR 4f , where each of R 4e and R 4f is independently hydrogen, hydroxyl, amino, nitro, thiol, or substituted or unsubstituted: C 1 -C 4 alkyl, alkoxy, or aryl,

Y is halogen, OCOR 7a , OR 7b , SR 7c , NR 7d R 7e , CO, NR 7f , PR 7g , AsR 7h R 7i R 7j , C≡CR 7k , substituted or unsubstituted: pyridine, imidazole, pyrazole, oxazole, thiazole, isoxazole, or quinoline, where each of R 7a , R 7b , R 7c , R 7d , R 7e , R 7f , R 7g , R 7h , R 7i , R 7j , and R 7k is independently acetylacetonate, pyridine, imidazole or substituted or unsubstituted: alkyl, alkenyl, alkynyl, aryl, or trisubstituted phosphine, and

p is 4.

4. The complex of claim 3 , wherein M is Pt(II) or Pd(II).

5. The complex of claim 3 , wherein R 1 , R 2 , R 3 , and R 5 are each independently hydrogen, halogen, hydroxyl, amino, or substituted or unsubstituted alkyl.

6. The complex of claim 3 , wherein R 1 , R 2 , R 3 , and R 5 are each independently hydrogen or substituted or unsubstituted alkyl.

7. The complex of claim 3 , wherein Y is halogen, OCOR 7a , OR 7b , NR 7d R 7e , CO, NR 7f , or PR 7g .

8. The complex of claim 3 , wherein Y is halogen.

9. The complex of claim 3 , wherein Ar 1 , Ar 2 , and Ar 3 are each independently a six-membered aryl or heteroaryl.

10. The complex of claim 3 , wherein Ar 1 is a six-membered heteroaryl.

11. The complex of claim 3 , wherein Ar 2 is a six-membered aryl.

12. The complex of claim 3 , wherein Ar 3 is a six-membered heteroaryl.

13. The complex of claim 3 , wherein Ar 1 , Ar 2 , and Ar 3 are each independently a five-membered aryl or heteroaryl.

14. The complex of claim 3 , wherein the complex is

15. A light emitting device comprising the complex of claim 14 .

16. A light emitting device comprising the complex of claim 3 .

17. An OLED device comprising the complex of claim 3 .

18. The OLED device of claim 17 , wherein the device is a phosphorescent OLED device.

19. A photovoltaic device comprising the complex of claim 3 .

20. A luminescent display device comprising the complex of claim 3 .