Synthesis, Crystal Structures and Photosensitizing Activities of Ni(II) and Pd(II) Heteroleptic Dithiolate-dppf Complexes

摘要

New heteroleptic complexes, [M(dithiolate-dppf)] (M=Ni(II) 1,Pd (II) 2, dithiolate=2-(methylene-1,1'-dithiolato)-1,3-indandione (L1); Pd(II) 3, 2-(methylene-1,1'-dithiolato)-5,5'-dimethylcyclohexane- 1,3-dione (L2); dppf = 1,1'-bis(diphenylphosphino)ferrocene) have been synthesized and characterized by elemental analysis, spectroscopy (IR, UV-Vis., 1H, 13C and 31PNMR) and cyclic voltammetry. X-ray crystallography revealed distorted square planar geometry with P2MS2 cores in 1-3, displaying M···HC intramolecular anagostic interactions. Complexes 1-3 show luminescent characteristics in CH2Cl2 solution at room temperature emanating from the MLCT charge-transfer state. Based on their optical and electrochemical properties, the sensitizing activities of 1-3 have been explored; the Ni complex 1 has shown significant light to electrical energy conversion efficiency with h value of 0.78%. All the three complexes with srt, 106-107 S cm1 and Ea=1.00-1.35 eV are weakly conducting but show semiconducting characteristic in the 303-363 K temperature range.