Chiral Supramolecular Microporous Thio-Oxomolybdenum(V) Tartrates for the Selective Adsorptions of Gases.

Two pairs of enantiomerically pure hexanuclear and tetranuclear microporous molybdenum(V) d/l-tartrates, (Htrz)[MoO(μ-O)(μ-S)(d/l-Htart)(Htrz)]·8HO (abbreviated as d- and l-; Htart = tartaric acid, Htrz = 1,2,4-triazole) and (H2-mim)[MoO(μ-S)(d/l-tart)]·4HO (d-/l-; H2-mim = 2-methylimidazole), have been isolated in reduced media and well characterized. These enantiomers are observed to finish self-assemblies with single chiral configurations. Structural analyses indicate that tartrates adopt different coordination modes with α-carboxy and/or α-alkoxy groups in and , which are further completed with nitrogen-containing ligands. There are two types of micropores that exist in and , separately, which are all formed by the isolated molecules themselves. The significant roles of hydrogen bonding among lattice molecules, tartrates, and multi-azoles are suggested, where and exhibited interesting supramolecular networks only through intramolecular self-sorts. Adsorption tests show that has good affinities toward CO and O, while is the most potential O adsorbent compared with other common gases CO, H, CH, and N under different pressures. In addition, IR, UV-vis, CD (circular dichroism), and solid-state C NMR spectroscopies have demonstrated the special chemical properties of these novel molybdenum d/l-tartrates.