LAUSR

Abstract Five new Anderson-type polyoxometalate-based metal–organic complexes, [Cu4(μ3-OH)2(H2O)6(4-dpye)2(TeMo6O24)]·2H2O (1), [Cu(4-dpyb)(CrMo6(OH)6O18)2(H2O)2][Cu(4-dpyb)(H2O)4](4-H2dpyb)·6H2O (2), H[Cu2(3-dpyb)2(C2O4)(CrMo6(OH)6O18)]·8H2O (3), [Cu2(4-dpyh)(CrMo6(OH)5O19)(H2O)8]·10H2O (4) and [Cu4(μ2-OH)(μ3-OH)(H2O)6(4-dpyh)(TeMo6O24)]·H2O (5) (4-dpye = N,N′-bis(4-pyridinecarboxamide)-1,2-ethane, 4-dpyb = N,N′-bis(4-pyridinecarboxamide)-1,4-butane, 3-dpyb = N,N′-bis(3-pyridinecarboxamide)-1,4-butane, 4-dpyh = N,N′-bis(4-pyridinecarboxamide)-1,6-hexane), were hydrothermally prepared and structurally characterized by single crystal X-ray diffraction analyses and characterized by single-crystal X-ray diffraction, elemental analysis, IR, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA). Complex 1 is a 2D network, which is constructed from Cu4–TeMo6 inorganic chains and 4-dpye ligands. Complex 2 contains two types of 1D chains. Complex 3 shows a 1D ring-like chain structure, in which the CrMo6 anions act as fourfold monodentate ligands consolidating the [Cu2(3-dpyb)2(C2O4)] rings. Complex 4 is a 0D structure containing a dinuclear complex cation [Cu2(4-dpyh)]4+ and discrete CrMo6 anion. Complex 5 exhibits a 3D framework constructed from 2D Cu4–TeMo6 inorganic layer and 4-dpyh ligands. The spacer lengths and N-donor sites of the bis-pyridyl-bis-amide ligands, as well as different polyoxometalates play important roles in tuning the structures of the title complexes. The electrochemical behavior and electrocatalytic properties, as well as the photocatalytic activities of the title complexes have been studied.