A photofunctional platform of bis-terpyridine ruthenium complex-linked coordination polymers with structural diversity

Abstract

Solvothermal syntheses of the bis(4′-carboxyl-2,2′:6′,2′′-terpyridine) ruthenium complex [Ru(tpyCOO⁻)₂] as a linker and different metal anions as nodes constructed a family of ten novel coordination polymers (CPs) with different topological types, ranging from one-dimensional (1D) chains and two-dimensional (2D) networks to three-dimensional (3D) frameworks. The structural diversity of CPs is achieved by the various coordinating geometries of metal nodes, including 3d transition (monometallic or bimetallic), lanthanide, and group 4 (zirconium and hafnium) metal anions. The Ru complex linker plays the role of a light-harvesting unit and renders multifarious photofunctions to the CP materials. While the ytterbium CP (Yb–Ru) exhibits near-infrared emission upon visible-light excitation, the 2D bimetallic Co/Ni CPs (Co_x–Ni_y–Ru) and 3D interpenetrated copper CP (Cu–Ru) show high to modest efficiencies toward the photocatalytic hydrogen evolution reaction. We suggest the series of new CPs with versatile structural traits as a unique platform for the research of photocatalysis and other photonic functional applications.