The One-step Synthesis And Controllable Assembly Of Anderson POMs Modified By TRIS

Polyoxometalates(POMs),which have been widely used in catalysis,medicine,magnetic materials,are an important topic of inorganic chemistry.Recently,the research on POM-based porous structures have developed rapidly and these materials have been applied in gas separation,adsorption and other fields,expanding the application of POMs.Anderson-type are the most flexible basic topological units in POMs due to their unique structural characteristics and easy modification,especially the Anderson-type POMs modified by trihydroxymethyl ligands(TRIS).In recent years,a large amount of POM-based functional materials prepared through the organic modification of TRIS-Anderson POMs have been reported and attracted broad attention.The TRIS-Anderson POMs were all synthesized by multi-step reactions.This research have developed a new and convenient protocol for the preparation TRIS-Anderson POMs by a one-pot hydrothermal procedure,which is totally different from the traditional method.Based on this method,a series of TRIS-Anderson POMs with different heteroatom have been synthesized,included an Anderson POMs with a tetravalent vanadium heteroatom for the first time,which opened up a new way for the synthesis of TRIS-Anderson POMs.The products were characterized by IR,NMR,MS,XPS and X-ray single crystal diffraction.The structural analysis revealed that the products exhibited novel 3D cage-like and framework structures built by TRIS-Anderson POMs.Furthermore,the main factors affecting the formation of the porous structures of TRIS-Anderson POMs were explored from the perspectives of synthesis methods,counterions and TRIS ligands.In particular,the effect of the size of terminal group of the TRIS ligand on the crystal stacking under the same synthetic conditions was discussed.The relationship between the three different TRIS ligands and the assemblies of their corresponding TRIS-Anderson POMs in crystal structures was successfully explained.These studies have provided valuable theoretical basis for the controllable design of new POM-based porous materials.