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, (H 2 trz) 3 [Mo 6 O 6 (μ 2 -O) 3 (μ 2 -S) 3 (d/l-Htart) 3 (Htrz) 6 ]·8H 2 O (abbreviated as d- 1 and l- 1 ; H 4 tart = tartaric acid, Htrz = 1,2,4-triazole) and (H 2 2-mim) 8 [Mo 4 O 4 (μ 2 -S) 4 (d/l-tart) 2 ] 2 ·4H 2 O (d- 2 /l- 2 ; 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 1 and 2 , which are further completed with nitrogen-containing ligands. There are two types of micropores that exist in 1 and 2 , 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 1 and 2 exhibited interesting supramolecular networks only through intramolecular self-sorts. Adsorption tests show that 1 has good affinities toward CO 2 and O 2 , while 2 is the most potential O 2 adsorbent compared with other common gases CO 2 , H 2 , CH 4 , and N 2 under different pressures. In addition, IR, UV-vis, CD (circular dichroism), and solid-state 13 C NMR spectroscopies have demonstrated the special chemical properties of these novel molybdenum d/l-tartrates.