Anion-Dominated Copper Salicyaldimine Complexes-Structures, Coordination Mode of Nitrate and Decolorization Properties toward Acid Orange 7 Dye.

Abstract

A salicyaldimine ligand, 3-tert-butyl-4-hydroxy-5-(((pyridin-2-ylmethyl)imino)methyl)benzoic acid (H2Lsalpyca) and two Cu(II)−salicylaldimine complexes, [Cu(HLsalpyca)Cl] (1) and [Cu(HLsalpyca)(NO3)]n (2), have been synthesized. Complex 1 has a discrete mononuclear structure, in which the Cu(II) center is in a distorted square-planar geometry made up of one HLsalpyca− monoanion in an NNO tris-chelating mode and one Cl− anion. Complex 2 adopts a neutral one-dimensional zigzag chain structure propagating along the crystallographic [010] direction, where the Cu(II) center suits a distorted square pyramidal geometry with a τ value of 0.134, consisted of one HLsalpyca− monoanion as an NNO tris-chelator and two NO3− anions. When the Cu∙∙∙O semi coordination is taken into consideration, the nitrato ligand bridges two Cu(II) centers in an unsymmetrical bridging-tridentate with a μ, κ4O,O′:O′,O″ coordination. Clearly, anion herein plays a critical role in dominating the formation of discrete and polymeric structures of copper salicyaldimine complexes. Noteworthy, complex 2 is insoluble but highly stable in H2O and various organic solvents (CH3OH, CH3CN, acetone, CH2Cl2 and THF). Moreover, complex 2 shows good photocatalytic degradation activity and recyclability to accelerate the decolorization rate and enhance the decolorization performance of acid orange 7 (AO7) dye by hydrogen peroxide (H2O2) under daylight.