Opto-electroactive device comprising a metallocene and method

1. An opto-electroactive device comprising

an anode;

a cathode; and

a layer comprising a metallocene of the formula

wherein M is zirconium or hafnium; X is halogen and R 1 –R 5 are each independently hydrogen, aryl, alkyl, halogen or —Si(R 6 ) 3 ; or wherein at least two adjacent R substituents on at least one ring are joined to form a fused ring, which may be unsubstituted or substituted with aryl, alkyl, halogen or —Si(R 6 ) 3 ; or wherein the R 1 substituents on each ring are joined via a bridging ansa group, and

wherein R 6 is an alkyl group, a substituted alkyl group, an aryl or a substituted aryl group.

2. The opto-electroactive device of claim 1 , wherein X is fluoro, chloro or bromo, and R 1 –R 5 are each hydrogen.

3. The opto-electroactive device of claim 1 , wherein X is fluoro, chloro or bromo, and the R 1 substituents on each ring are joined to link the rings via a bridging ansa group, wherein the bridging ansa group is -E(R 6 ) 2 wherein E is carbon, silicon, or germanium, and R 6 is selected from the group consisting of alkyl, substituted alkyl, methyl, aryl and substituted aryl.

4. The opto-electroactive device of claim 3 , wherein X is chloro and E is silicon.

5. The opto-electroactive device of claim 1 , which comprises a zirconocene.

6. The opto-electroactive device of claim 5 , wherein the zirconocene has a HOMO value of less than or equal to minus 6 electron volts.

7. The opto-electroactive device of claim 5 , wherein the zirconocene is phosphorescent.

8. The opto-electroactive device of claim 1 , which comprises a hafnocene.

9. The opto-electroactive device of claim 1 , which is an electroluminescent device, an LED, an OLED, a photovoltaic device, a photoconductor, a photodetector, or in a chemical or biochemical sensor.

10. The opto-electroactive device of claim 1 , wherein the metallocene is present in a light-emitting layer and the device emits light in the wavelength range of about 300 nm to about 1200 nm; or wherein the metallocene is present in a hole-blocking layer.

11. The opto-electroactive device of claim 1 , wherein the metallocene is present in a light-absorbing layer and the device absorbs light in the wavelength range of about 300 nm to about 1200 nm.

12. The opto-electroactive device of claim 1 , wherein the metallocene is present in the form of a composite comprising at least one metallocene and at least one polymeric or non-polymeric conductor.

13. The opto-electroactive device of claim 12 , wherein the polymeric conductor comprises at least one of poly(9-vinylcarbazole) or poly(phenylsilane).

14. The opto-electroactive device of claim 12 , wherein the non-polymeric conductor at least one of an aryl-substituted oxadiazole, an aryl-substituted phenanthroline, a benzoxazole, a benzthiazole, an aryl-substituted triazole, or 3-(4′-tert-butylphenyl)-4-phenyl-5-(4′-biphenyl)-1,2,4-triazole.

15. An opto-electroactive device comprising: (a) an anode; (b) a cathode; and (c) a layer comprising a zirconocene of the formula

wherein X is halogen and R 1 –R 5 are each independently hydrogen, aryl, alkyl, halogen or —Si(R 6 ) 3 ; or wherein at least two adjacent R substituents on at least one ring are joined to form a fused ring, which may be unsubstituted or substituted with aryl, alkyl, halogen or —Si(R 6 ) 3 wherein R 6 is an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; or wherein the R 1 substituents on each ring are joined to link the rings via a bridging ansa group; and

wherein the layer (c) is a light-emitting layer and the device emits light in the wavelength range of about 300 nm to about 1200 nm; or wherein the layer (c) is a light-absorbing layer and the device absorbs light in the wavelength range of about 300 nm to about 1200 nm; or wherein the layer (c) is a hole-blocking layer.

16. The opto-electroactive device of claim 15 , wherein X is fluoro, chloro or bromo, and R 1 –R 5 are each hydrogen.

17. The opto-electroactive device of claim 15 , wherein X is fluoro, chloro or bromo, and the R 1 substituents on each ring are joined to link the rings via a bridging ansa group, wherein the bridging ansa group is —Si(R 6 ) 2 wherein R 6 is selected from the group consisting of alkyl, substituted alkyl, methyl, aryl and substituted aryl.

18. The opto-electroactive device of claim 15 , which is an electroluminescent device, an LED, an OLED, a photovoltaic device, a photoconductor, a photodetector, or in a chemical or biochemical sensor.

19. The opto-electroactive device of claim 15 , wherein the zirconocene is phosphorescent.

20. The opto-electroactive device of claim 15 , wherein the zirconocene is present in the form of a composite comprising at least one zirconocene and at least one polymeric or non-polymeric conductor.

21. The opto-electroactive device of claim 20 , wherein the polymeric conductor comprises at least one of poly(9-vinylcarbazole) or poly(phenylsilane).

22. The opto-electroactive device of claim 20 , wherein the non-polymeric conductor comprises at least one of an aryl-substituted oxadiazole, an aryl-substituted phenanthroline, a benzoxazole, a benzthiazole, an aryl-substituted triazole, or 3-(4′-tert-butylphenyl)-4-phenyl-5-(4″-biphenyl)-1,2,4-triazole.

23. A method for making an opto-electroactive device comprising a zirconocene of claim 1 , which comprises the step of applying the metallocene by vacuum deposition or from solution.

24. A method for making an opto-electroactive device comprising a zirconocene of claim 15 , which comprises the step of applying the zirconocene by vacuum deposition or from solution.