<div><p></p><p>Two new isopolymolybdate-based metal-organic complexes, [Cu<sub>2</sub>(2-ptz)<sub>2</sub>(Mo<sub>4</sub>O<sub>14</sub>)<sub>0.5</sub>] (<b>1</b>) and [Cu<sub>3</sub>(OH)<sub>2</sub>(3-ptz)<sub>4</sub>(纬-H<sub>4</sub>Mo<sub>8</sub>O<sub>26</sub>)(H<sub>2</sub>O)<sub>4</sub>]路10H<sub>2</sub>O (<b>2</b>) (2-ptzH = 5-(2-pyridyl)-1H-tetrazole, 3-ptzH = 5-(3-pyridyl)-1H-tetrazole), constructed from isomeric ligands with different N-donor sites were synthesized under hydrothermal conditions. In <b>1</b>, each [Mo<sub>4</sub>O<sub>14</sub>]<sup>4-</sup> cluster connected with six neighboring [Mo<sub>4</sub>O<sub>14</sub>]<sup>4-</sup> clusters through six binuclear [Cu<sub>2</sub>(2-ptz)<sub>2</sub>]<sup>2+</sup> subunits to yield a two-dimensional (2D) layer. In <b>2</b>, bidentate inorganic [Mo<sub>8</sub>O<sub>26</sub>]<sup>4-</sup> anions link the trinuclear [Cu<sub>3</sub>(OH)<sub>2</sub>(3-ptz)<sub>4</sub>] clusters to construct a 1D chain. Adjacent chains connect through Mo-N bonds between the [Mo<sub>8</sub>O<sub>26</sub>]<sup>4-</sup> anions and pyridyl groups from the trinuclear clusters to form a 2D layer. The effect of the N-donor sites of the rigid isomeric ligands on the structures of <b>1</b> and <b>2</b> was discussed. The electrochemical properties and photocatalytic activities of <b>1</b> and <b>2</b> have also been studied.</p></div
