Single-Crystal-to-Single-Crystal Cluster Transformation in a Microporous Molybdoarsenate(V)-Metalorganic Framework

[Image: see text] The hybrid compound [Cu(cyclam)(H(2)O)(2)](0.5)[{Cu(cyclam)}(1.5){B-H(2)As(2)Mo(6)O(26)(H(2)O)}]·9H(2)O (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane) was synthesized in aqueous solution by reacting the {Cu(cyclam)}(2+) complex with a mixture of heptamolybdate and an arsenate(V) source. Crystal packing of 1 exhibits a supramolecular open-framework built of discrete covalent molybdoarsenate/metalorganic units and additional [Cu(cyclam)(H(2)O)(2)](2+) cations, the stacking of which generates squarelike channels parallel to the z axis with an approximate cross section of 10 × 11 Å(2) where all the hydration water molecules are hosted. Thermal evacuation of solvent molecules yields a new anhydrous crystalline phase, but compound 1 does not preserve its single-crystalline nature upon heating. However, when crystals are dehydrated under vacuum, they undergo a structural transformation that proceeds via a single-crystal-to-single-crystal pathway, leading to the anhydrous phase [{Cu(cyclam)}(2)(A-H(2)As(2)Mo(6)O(26))] (2). Total dehydration results in important modifications within the inorganic cluster skeleton which reveals an unprecedented solid-state B to A isomerization of the polyoxoanion. This transition also involves changes in the Cu(II) bonding scheme that lead to covalent cluster/metalorganic layers by retaining the open-framework nature of 1. Compound 2 adsorbs ambient moisture upon air exposure, but it does not revert back to 1, and the hydrated phase [{Cu(cyclam)}(2)(A-H(2)As(2)Mo(6)O(26))]·6H(2)O (2h) is obtained instead. Structural variations between 1 and 2 are reflected in electron paramagnetic resonance spectroscopy measurements, and the permanent microporosity of 2 provides interesting functionalities to the system such as the selective adsorption of gaseous CO(2) over N(2).