Weak interaction-steered evolution of polyoxovanadate-based metal-organic polyhedra from transformation via interlock to packing

A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high stability,weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design.In this endeavor,a ligand-dominated strategy that embodies tunable electrostatic repulsion andπ···πstacking was first employed to shape polyoxovanadate-based metal-organic polyhedra(VMOPs).Structural evolution involving transformation,interlock,and discovery of an unprecedented prototype of the Star of David was hence achievable.Not only as a handy tool for the primary structural control over VMOPs,these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors,representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.

Engineering in amino acid-functionalized double-layer heteropolymolybdates:from structural control to catalytic activity

A reexamination of the structural constraints on the amino acid-functionalized heteropolymolybdates has afforded four polyanions,namely the double-layer [(SeO_(3))_(2)Mo_(12)O_(36)(CH_(3)COO)_(3)]^(7-)(1),[(SeO_(3))_(1.3)(HPO_(3))_(0.7)Mo_(12)O_(36)(NH_(3)CH_(2)COO)_(3)]^(4-)(2),[(SeO_(3))_(1.4)(HPO_(3))_(0.6)Mo_(12)O_(36)(LNH_(3)C_(2)H_(3)OHCOO)_(3)]^(4-)(3),and the mono-layer [(SeO_(3))-Mo_6O_(18)(L-NH_(3)C_(2)H_(3)OHCOO)_(3)]^(2-)(4),which were crystallized as the hydrated ammonium salts.