Crystalline porous ionic salts assembled from polyoxometalates and cationic capsule for the selective photocatalytic aerobic oxidation of aromatic alcohols to aldehydes

Crystalline porous ionic salts(CPISs) represent a new type of porous materials constructed by electrostatic interaction, however, synthesis of CPISs bearing pre-designed functionality while exhibiting permanent porosity is still challenging. Herein we report the facile synthesis of a series of CPISs 1-3 built from photocatalytic-active polyoxometalate(POM) clusters and cationic Zr-based capsules, which showed open porous frameworks with BET surface area up to 33 m^(2)/g and high activity and selectivity for photodriven aerobic oxidation of alcohols to aldehydes. Compared with the pristine POM cluster {W10}, 1 can promote the reaction in much higher efficiency due to the concerted catalysis of preinstalled {W10} and Zr-based capsule together with open channels. This work highlights the advantage of CPISs as porous heterogeneous catalysts in organic transformation, and may shed light on the rational design of more delicate CPISs-derived functional materials.

Sulfonate-Functionalized Polyoxovanadate-Based Metal-Organic Polyhedra for Enhanced Proton Conduction via the Synergy of Linker and Metal Cluster Vertex

Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V_(5)O_(9)Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Coupled with the proton-conductive{V_(5)O_(9)Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10^(-2)S cm^(-1)at 65℃under 90%RH,recording the highest value for MOPs pellet sample.This value is enhanced~1order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.

Additive-Mediated Selective Oxidation of Alcohols to Esters via Synergistic Effect Using Single Cation Cobalt Catalyst Stabilized with Inorganic Ligand

The direct catalytic oxidation of alcohols to esters is very appealing,but the economical-friendly catalysis systems are not yet well established.Herein,we show that a pure inorganic ligand-supported single-atomic cobalt compound,(NH_(4))_(3)[CoMo_(6)O_(18)(OH)_(6)](simplified as CoMo_(6)),could be used as a heterogeneous catalyst and effectively promote this type of reaction in the presence of 30%H_(2)O_(2)using KCl as an additive.The oxidative cross-esterification of various alcohols(aromatic and aliphatic)could be achieved under mild conditions in nearly all cases,affording the corresponding esters in high yields,including several drug molecules and natural products.Detailed studies have revealed that chloride ion is able to bind to the CoMo_(6)to form a supramolecular dimer 2(CoMo_(6)∙Cl),which can effectively catalyze the reaction via a synergistic effect from chloride ion and CoMo_(6).Mechanism studies and control reactions demonstrate that the esterification proceeds via the key oxidative immediate of aldehydes.