A series of germanotungstate-based 3d-4f heterometallic compounds with visible-light induced photocatalytic, electrochemical and magnetic properties

Abstract

A series of 3d-4f heterometallic germanotungstate dimers {[Cu(dap)(H2O)3][LnCu3(dap)3(OH)3(H2O)2(GeW11O39)]}⋅nH2O (Ln = SmⅢ, n = 11 (1), EuⅢ, n = 12 (2), GdⅢ, n = 10 (3) and TbⅢ, n = 13 (4); dap = 1, 2-diaminopropane) have been prepared under hydrothermal conditions and structurally characterized by IR, UV–Vis, XRD, and X-ray single-crystal diffraction. Compounds 1–4 are essentially isomorphic and display organic-inorganic hybrid dimeric structures consisting of [LnCu3(dap)3(OH)3(H2O)(GeW11O39)]24− with two supporting [Cu(dap)(H2O)3]2+ cations on both sides. The four compounds all exhibit the excellent photocatalytic activities to degradation of methylene blue (MB) and rhodamine-B (RhB) under visible light irradiation in the presence of H2O2. Additionally, 1–4 displays an apparent electrocatalytic activity for the reduction of hydrogen peroxide. The variable-temperature magnetic studies show that the magnetic behaviours of 1, 2 and 4 are dominated by antiferromagnetic coupling interactions, while that of 3 is ferromagnetic interactions coexist along with antiferromagnetic interactions.