A Deep Insight into the Photoluminescence Properties of Schiff Base Cd^II and Zn^II Complexes

Abstract

A tridentate N,N,O donor ligand 2,4-dichloro-2-[(2-piperazine-4-yl-ethylimino)-methyl]-phenol (HL) was designed, and eight new Zn^II and Cd^II complexes, namely, [Zn(LH)(SCN)₂] (1), [Zn(LH)(N₃)₂] (2), [Zn(LH)(NO₂)₂] (3), [Zn(LH)(dca)(OAc)] (4), [Cd₂(LH)₂(SCN)₄] (5), [Cd(LH)(N₃)₂] (6), [Cd(LH)(NO₂)₂] (7), and [Cd(LH)(dca)(OAc)] (8) [where dca = dicyanamide anion] were synthesized. Five of them (1, 2, 4, 5, 7) were structurally characterized through single-crystal X-ray diffraction analysis. H-Bonding interactions are found to be the major stabilizing factor for crystallization in the solid state. Experimental and computational studies were performed in cooperation to provide a rationalization of the photoluminescence properties of those complexes. The quantum yields are anion-dependent, with enhanced efficiencies in the following order: LH < Cd-SCN(5) < Cd-dca(8) < Cd-N₃(6) < Cd-NO₂(7) < Zn-dca(4) < Zn-N₃(2) < ZnNO₂(3) < ZnSCN(1). By using quantum chemical calculations we rationalized the above trends. Moreover, the diverse lifetimes observed for those eight complexes were also quantitatively explained by considering the subtle competition between different photo-deactivation pathways.