Spatially Confined Construction of Ultrasmall Pd Clusters Within Nitro-Bonded Covalent Organic Frameworks for Efficient Alkyne Semihydrogenation.

Confinement of metal species in porous supports is an effective strategy to optimize hydrogenation performance ascribing to tunable nanopore environments. However, only focusing on the electronic structure modulation for metal species has limited the design of improved catalysts. Herein, spatial confinement strategy is reported for constructing ultrasmall metal clusters in nitro-bonded COF (M@TpPa-NO, M = Pd, Pt, Ru, Rh, Ir).

Coordination Defect-Induced Frustrated Lewis Pairs in Polyoxo-metalate-Based Metal-Organic Frameworks for Efficient Catalytic Hydrogenation.

Precise control of the structure and spatial distance of Lewis acid (LA) and Lewis base (LB) sites in a porous system to construct efficient solid frustrated Lewis pair (FLP) catalyst is vital for industrial application but remains challenging. Herein, we constructed FLP sites in a polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes (LA) and surface-basic POM with abundant oxygen (LB). The well-defined and unique spatial conformation of the defective POM-based MOF ensure that the distance between LA and LB is at ~4.

Design of a Polyoxometalate-Based Metal-Organic Framework for Photocatalytic C(sp)-H Oxidation of Toluene.

A powerful and promising route for developing novel photocatalysts for light-driven toluene oxidation in water under mild conditions is presented. Herein, a novel polyoxometalate-based metal-organic framework (POMOF), , is prepared by incorporating the unusual Co-sandwiched POM anion [Co(μ-OH)(SiWO)] () and the photoactive organic bridging link ,'-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) into a framework. is a good candidate for photocatalytic water oxidation.

A hydrophilic inorganic framework based on a sandwich polyoxometalate: unusual chemoselectivity for aldehydes/ketones with in situ generated hydroxylamine.

A hydrophilic inorganic porous catalyst was prepared via the hydrothermal method. The combination of [WZn(HO)(ZnWO)] and Co(ii) provides a synergistical catalytic way to promote oximation of aldehyde/ketone with in situ generated hydroxylamine that initially produces an oxime, which further either dehydrates into a nitrile or undergoes a Beckmann rearrangement to form an amide.