| In this paper,two different types of new polyoxometalates-organic hybrid materials(Keggin type and Bielefeld ring type)are synthesized using hydrothermal method and conventional method,respectively,and characterized.Some innovative achievements of the paper are listed below:1.Twoα-keggin type phosphormolybdate based organic-inorganic hybrid materials of 4- and 5-electron reduced forms,respectively,by reactingα-keggin phosphomolybdic acid with organic molecules in presence of mental ions have been hydrothermally synthesized and characterized thoroughly.(1)Under the induction of copper ions,we hydrothermally synthesized for the first time a four-electron reducedα-keggin structure phosphormolybdic-based organic-inorganic hybrid materials from phosphormolybdic withα-keggin structure and 1,6-diaminohexane (HMD):(HMDH2)3(HPMo12O40).The induction of the copper ion and the effect of HMD for formation of the title compound are discussed.Organic molecular HMD are act as template and reducing agent.(2)Under the existance of nickel ion we hydrothermally synthesized a five-electron reducedα-keggin phosphormolybdate based organic-inorganic hybrid materials by reacting phosphormolybdic acid withα-keggin structure and caffeine.The properties of it are characterized in detail.2.We studied surface modification of the Bielefeld ring via molecular designing and self-Assembly.Some innovative achievements are as follows:(1)By reacting tyrosine acid and glutamic acid as modifiers with simple inorganic salts under acidic condition in preaence of reducing agent,we got two new type polyoxometalates-based organic inorganic hybrid material of the formula Na8Co3[MoⅥ126MoⅤ28O462H14(H2O)46(HOC6H4-CH2CH(NH3+)COO-)12]·xH2O(x≈200)and Na2Gd4[MoⅥ126MoⅤ28O462H14 -(H2O)42(HOOCCH2CH2CH(NH3+)COO-)14]·xH20(x≈300).The two new compounds have been characterized in dedail by means of single crystal X-ray structure analyzing and so on.The result showed that the carboxyl groups of amino acids coordinate to {Mo2} units in the Bielefeld ring and form a type of huge ring-shaped organic/inorganic hybrids.(2)Experimental results indicate that these two compounds have semiconductor properties.Meanwhile,the third-order nonlinear optical properties of the compounds were studied with Z-scan technique by using 18 ps laser pulse at the wavelength of 532 nm.The result showed they have large positive third-order nonlinear refractive coefficient and a self-focusing property.These compounds possess potential application prospect in view of new optical materials.
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