Study On Host-Guest Molecular Design And Properties Of Polyoxometalate-Calixarene Based Hybrid Materials

Polyoxometalates show rich diversity of structures and functions as diverse family of metal-oxygen clusters. It’s significant for polyoxometalate modification that introduction organic molecular with functional groups into polyoxometalates to enhance varies newly of polyoxometalates based inorganic-organic functional hybrid materials. Calixarene is considered as the third generation of host compounds after crown ether and cyciodextrin, which has three-dimensional structure of adjusted cavity and easy modifiability both at upper and lower rims.Calixarene has varies applied in catalysis chemistry, ion recognition, nano-materials and supermolecular assembly field, and proves to be the prior chose as the new host compound.It’s always difficult for covalent modification of polyoxometalate as its easy clusters and its poor load stability. In this paper, we synthesis and design the calixarene derivates with functional groups by covalent modified with calixarene. The hybrid materials with unique structure and function are formed by covalent modification and electrostatic interaction of calixarene derivates and polyoxometalate. Firstly, we choose the vacancy polyoxometalate SiW11([N(C4H9)4]4SiW11O40(SiCH2CH2CH2N3)2)with azide group reacted with the calixarene derivates with alkynes group through Husigen cycloaddition to form the new hybrid material based on SiW11and calixarene, and characterized by FT-IR,1H NMR, Elemental Analysis and UV-Vis. We also have research on corrosion inhibitor of the hybrid material through testing for its electrochemical properties.On the basic of above studies, we introduce the calixarene with methylol group into Dawson type P2W15V3((Bu4N)5H4P2W15V3O62) and the structure of hybrid materials has been characterized by FT-IR,1H NMR, Elemental Analysis, ESI-MS. This is the first time to prepare the supermolecular compound based on Dawson type and calixarene derivate.Additionally, the inorganic-organic hybrid materials have been synthesized by electrostatic interaction of calixarene ionic liquid with different alkyl chains and sandwich type EuW10(Na9EuW10036·32H20), and characterize by FT-IR,1H NMR, TGA. It’s said that EuW10has good catalytic performance in extractive catalytic oxidative desulfurization, so we also research the catalysis application of hybrid material in oil desulfurization, and show good desulfurization results.