Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin-Based Open Frameworks.

Abstract

Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo8S8O8(OH)8(guest)]2- complex, formed by the self-condensation of four [MoV 2O2S2]2- fragments around a guest unit (MoVIO6H4 or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids. These new compounds were thoroughly characterized using X-ray diffraction (both powder and single-crystal), N2 adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using 1H NMR titration and small-angle X-ray scattering (SAXS) demonstrated pre-association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.