*Molecular structure, *Gas absorption & adsorption, *Ethylenediamine, *Cobalt, *Ionic crystals, *Tungsten compounds, *Chemical reactions, *X-ray diffraction

Seven new ionic solids built on polyoxometalate anions and [Co(en)3]3熫抢, namely, [Co(en)3Mo8O26(H3O)(Cl)](DMF)4(H2O) (Co-Mo8-DMF), [α-PW12O40][Co(en)3]·6DMF (Co-W12P-DMF), [α-PW12O40][Co(en)3]·6DEF (Co-W12P-DEF), [α-PMo12O40][Co(en)3]·5.5DMF (Co-Mo12P-DMF), [α-PMo12O40][Co(en)3]·6DEF (Co-Mo12P-DEF), [α-SiW12O40][Co(en)3]3/2[Cl]1/2·6DMF·3H2O (Co-W12Si-DMF), and [α-SiW12O40][Co(en)3]·6DEF (Co-W12Si-DEF), have been synthesized from nonaqueous (DMF/DEF) media and characterized by single-crystal X-ray diffraction. We attempt to understand if [Co(en)3]3熫抢 used in these reaction systems play a crucial role in controlling the assembly of these crystals. These ionic solids, after removal of the DMF or DEF molecules, are found to exhibit size selective H2adsorption properties over N2. The amount of hydrogen adsorption was influenced by POM anion types and their orientations. CoMo12P-DEF has the highest (0.9 wt %) H2uptake, and CoW12P-DEF has the lowest (0.4 wt %) uptake among the series when the adsorbate pressure approached 1 atm. [ABSTRACT FROM AUTHOR]

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