Series of Inorganic–Organic Hybrid Materials Constructed From Octamolybdates and Metal–Organic Frameworks: Syntheses, Structures, and Physical Properties

Series of inorganic–organic hybrid materials based on octamolybdates, silver ions, and multidentate N-donor ligands, namely, [Ag₂(2,3′-tmbpt)­(β-Mo₈O₂₆)_0.5] (<b>1</b>), [Ag₂(2,4′-tmbpt)₂(α-Mo₈O₂₆)_0.5(H₂O)_0.5]·2H₂O (<b>2</b>), [Ag₃(3,3′-tmbpt)₂(α-H₂Mo₈O₂₆)_0.5(β-Mo₈O₂₆)_0.5]·3.5H₂O (<b>3</b>), [Ag₂(3,3′-tmbpt)­(ε-Mo₈O₂₆)_0.5]·1.75H₂O (<b>4</b>), [Ag₂(3,4′-tmbpt)₂(β-Mo₈O₂₆)_0.5]·0.5H₂O (<b>5</b>), and [Ag­(3,4′-Htmbpt)­(β-Mo₈O₂₆)_0.5] (<b>6</b>), where 2,3′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)­methyl)-3-(3-pyridyl)-5-(2-pyridyl)-1,2,4-triazole), 2,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)­methyl)-3-(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole), 3,3′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)­methyl)-3,5-bis­(3-pyridyl)-1,2,4-triazole, and 3,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)­methyl)-3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole) have been synthesized under hydrothermal conditions. Compound <b>1</b> displays a rare 3D (3,4,8)-connected net with (4·8²)­(4²·8⁴)­(4³·8²⁰·10⁵) topology. Compound <b>2</b> shows a rare 3D (4,6)-connected self-catenated framework with (6⁴·8²)­(4²·6³·8²)­(4²·6⁸·8⁴·10) topology. Compound <b>3</b> is a scarce 3D framework based on two different kinds of [Mo₈O₂₆]^4– isomers. Compound <b>4</b> exhibits a 3D framework constructed by silver–organic sheets and the rare [ε-Mo₈O₂₆]^4– anions. Compound <b>5</b> shows an interesting 1D → 2D polythreaded structure. Compound <b>6</b> displays a 2D layer structure, which is further linked by the N–H···O hydrogen bonds to form a 3D supramolecular architecture. Their structures have been further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), electrochemistry and photoluminesce. Moreover, the photocatalytic activities for degradation of organic pollutant have been investigated for compounds <b>3</b>–<b>6