Two octamolybdate hybrid complexes based on flexible bis-pyridyl-bis-amide ligands with different spacer lengths, namely, {[Cu(L1)(β-Mo8O26)0.5(H2O)2]·H2O}n (1), [Cu(L2)(β-Mo8O26)0.5(H2O)] (2) (L1 = N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, L2 = N,N′-bis(3-pyridinecarboxamide)-1,6-hexane), have been successfully synthesized. Crystal structure analysis reveals that 1 is a two-dimensional (2D) network constructed from [Cu-L1]n2n+ chains and [β-Mo8O26]n4n− anions, displaying a 4-connected framework with 32·62·72 topology. Compound 2 consists of double one-dimensional (1D) meso-helical chains and 1D inorganic chains to generate a three-dimensional (3D) framework with a (4,4)-connected (4·64·8)2(42·62·82) topology. The title compounds represent the first examples of introducing a flexible bis-pyridyl-bis-amide ligand into the isopolymolybdates system. In addition, the electrochemical behavior of 1, luminescent properties and photocatalytic activities of the title compounds have been investigated.
