【摘要】 合成了三种具有Keggin结构的硅钨氧簇化合物 :K3 H [SiWⅥ12 O40 ]· 3H2 O (Ⅰ ) ,(H3 O ) 4[H3 SiWⅥ9WⅤ3 O40 ]·2H2 O(Ⅱ )和 [(CH3 ) 4 N]4[SiWⅥ12 O40 ]·4 5H2 O(Ⅲ ) ,用FTIR ,NIRFT Raman ,UV Vis和荧光光谱等研究手段进行了光谱研究 ,探讨其结构与性能的关系。在这些化合物中 ,阴离子相同或类似 ,具有孤立的 [SiW12 O40 ]簇骼基元 ,通过静电作用和弱的氢键与阳离子及水相连。它们的FTIR和NIRFT Raman光谱研究表明 :硅钨酸盐的特征振动频率与其结构相关 ,由于化合物Ⅱ中的部分W6+已被还原成W5+,使νas(W Od )振动频率降低 ,且簇阴离子电荷大小也明显地对νas(W—Oc—W ) ,νas(Si—Oa) ,δ(Oa—Si—Oa)等产生影响 ;化合物Ⅰ和Ⅱ的UV Vis光谱显示 ,在 2 0 0和 2 5 0nm左右有紫外吸收谱带 ;化合物Ⅰ的稳态荧光光谱观察到分别以 2 2 0 ,35 0和 4 4 0nm激发时 ,相应在 35 0 ,4 4 0和 5 2 0及 6 75nm左右产生一个或两个发射峰。更多还原

【Abstract】 Three compounds of tungstosilicic acid and tungstosilicic salt: K₃H[SiW^Ⅵ 12 O₄0 ]·3H₂O（Ⅰ）,（H₃O）₄[H₃SiW^Ⅵ₉W^Ⅴ₃O₄0 ]·2H ₂O（Ⅱ） and [（CH₃）₄N]₄[SiW^Ⅵ₁2 O₄0 ]·4.5H₂O（Ⅲ）,wit h Keggin structure,have been synthesized. The relationship between their proper ties and structures was studied by using FTIR,NIR FT-Raman,UV-Vis and fl urescence etc. They possess isolated [SiW₁2 O₄0 ] cage anion,wh ich combines with cation and water by static electric action and weak hydrog en bond;The study of their FTIR and Raman spectra shows that the vibr atio nal frequencies of the group are related to the structure of the materials. For the compoundⅡ,the vibrational frequency of ν _as （W O_d） decreases as part of W⁶+ are redu ced to W⁵+ ,and the charges of anion group affect ν _as （W-O c-W） ,ν _as （Si-O_a） and δ （O_a-Si-O_a） etc. apparently . I n UV-Vis spectra of compound Ⅰ and Ⅱ,there are two characteristic peaks a t 200 and 260 nm,respectively. The fluorescence spectra of comp ound Ⅰ were studied,and showed that the emission peak is at 350,440 ,520 and 675 nm excited by 220,350 and 440 nm.更多还原