D7 /d8 Metal Complexes Constructed from 2,6-Bis(2-benzimidazolyl)pyridyl or 2,6-Di-(pyrazol-3-yl)pyridine Derivatives: Synthesis, Structure, Characterization, and Photocatalytic Activity.

Abstract

By introducing 2,6-bis(2-benzimidazolyl)pyridyl and 2,6-di-(pyrazol-3-yl)pyridine derivatives as ligand in the reaction system, three new transition-metal coordination complexes have been successfully synthesized, namely, [Co(HL1 )2 ] (1), [Ni(HL1 )2 ] (2), and [Ni3 (H2 L2 )2 ⋅(HL2 )2 ]⋅(OH)3 ⋅(Ac)⋅H2 O (3) (H2 L1 =2,6-bis(benzimidazol-2-yl)pyridine and H2 L2 =2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine). They are all characterized by elemental analysis, IR spectroscopy, UV absorption spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analysis shows that the structures of complexes 1 and 2 are similar. They are constructed from one metal (Co, Ni) atom and two 2,6-bis(benzimidazol-2-yl)pyridine ligands (HL1 - ); the HL1 - ligand is in the tridentate coordination mode with N3 donors. Complex 3 is a trinuclear Ni complex with four 2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine (H2 L2 ) ligands, in which the H2 L2 possesses two coordination fashions: terminal tridentate and bridging tetradentate. In addition, the surface photovoltage spectroscopy and photocatalytic activities of complexes 1-3 were investigated in detail. The results reveal that complex 3 possesses higher photocatalytic activity.