In-situ Growth of Metallocluster inside Heterometal-organic Cage to Switch Electron Transfer for Targeted CO2 Photoreduction.

Construction of metal-organic cages (MOCs) with internal modifications is a promising avenue to build enzyme-like cavities and unlocking the mystery of highly catalytic activity and selectivity of enzymes. However, current interests are mainly focused on single-metal-node cages, little achievement has been expended to metalloclusters-based architectures, and the in situ endogenous generation of metal clusters. Herein, based on the hard-soft-acids-bases (HSAB), the metalloclusters-based heterometallic MOC (Cu3VMOP) constructed of [Cu3OPz3]+ and [V6O6(OCH3)9(SO4)(CO2)3]2- clusters was obtained by one-pot method.

Two High-Nuclear Wheel-Hub-Shaped Transition-Metal-Doped Polyoxovanadates.

The first two unprecedented high-nuclear wheel-hub-shaped transition-metal-doped polyoxovanadates, [MMoWVP] [M = Ni (), Co ()], have been assembled under solvothermal conditions. The center of the cluster consists of two {Ni(oa)} rings as the center hole, four {MoO} units acting as the spokes, and four {WV(PPOA)} molecular building blocks serving as the tire. Compound exhibits good catalytic properties and recyclability in oxidative desulfurization reactions.

Endohedral Functionalization for Structural Transformation of Polyoxovanadate-Based Metal-Organic Cube.

Functionalized internal modifications of metal-organic polyhedra (MOPs) can endow properties and functions different from the original ones. Until now, there have been only a few examples of endohedral modifications of polyoxovanadate-based MOPs. Herein, an efficient coordination-driven strategy was chosen for the inner modification of two metal-organic cubes (MOCs) with different sizes, and , constructed from polyoxovanadate clusters [VO(OCH)(SO)(CO)] SBU and tetradentate ligands.