Metal-Directed Self-Assembly of {Ti₈L₂} Cluster-Based Coordination Polymers with Enhanced Photocatalytic Alcohol Oxidation Activity

Abstract

Cooperative assembly of the neutral cluster {Ti₈O₅(OEt)₁₈L₂} (L = pyrazine-2,3-dicarboxylic acid) with different metal units of Mn(NO₃)₂, CuCl₂, Zn(OEt)₂, Cd(NO₃)₂, Ce(NO₃)₃, Lu(NO₃)₃, and Lu(NO₃)₂(OEt), or the [Cu₂I₂] cluster, generates a family of titanium-oxygen cluster (TOC)-based coordination polymers. These one-dimensional (1D) linear structures contain the same {Ti₈L₂} cluster but with variable bridging metal units. The regulation of the heterometal not only affects the chain geometries of the {MTi₈} but also affects the way the 1D chains are stacked in the crystal lattice. Investigation of the catalytic activities toward alcohol oxidation demonstrated the synergetic effect of combining the metal site and the photosensitive {Ti₈L₂} cluster in the tailored structure. Under light illumination, the {MTi₈} with dual catalytic sites shows greatly enhanced catalytic activity in the selective oxidation of alcohols to aldehydes. Because the compositions and structures of {MTi₈} are highly tunable, this work spotlights the potential of utilizing such metal-bridged multidimensional Ti-oxo materials for cooperative photoredox catalysis for organic transformation.