【作者】 叶燕珠；

【导师】 林深；

【作者基本信息】 福建师范大学 ， 物理化学， 2005， 硕士

【摘要】 以Keggin结构的磷钼酸为电子对受体,以有机胺类为电子对给体合成了五种光致变色电荷转移盐:[（C₂H₄OH）₂NH₂]₃·[PMo₁2O₄0]·2H₂O（1）,[（C₂H₄OH）₃NH]₂·[HPMo₁2O₄0]·3H₂O（2）,[（CH₃）₃CNH₃]₃[PMo₁2O₄0]·2H₂O（3）,[（C₆H₅）（CH₃）₂NH]₃·[PMo₁2O₄0]·1.5H₂O（4）和[（C₁0H₈N₂H₂）]·[HPMo₁2O₄0]·H₂O（5）,并用用X射线单晶衍射、IR、紫外、固体漫反射电子光谱、ESR等手段进行了表征。X射线单晶衍射结果及IR光谱表明,合成的化合物仍保持杂多阴离子的Keggin结构,但骨架有轻微的畸变。固体漫反射电子光谱及低温电子顺磁共振（ESR）结果表明,化合物（1）、（2）、（3）在光的激发下分子内有机阳离子和杂多阴离子之间发生了电荷转移,具有光致变色性。 本论文还设计合成了两种新型的以多金属氧酸盐为构筑块的有机-无机复合物[（PW₁2O₄0）{Zn（C₁0H₈N₂）₂（H₂O）}]·1.5[Zn（C₁0H₈N₂）₃]·2（OH^-）·H₂O、[Zn（C₁0H₈N₂）₃][PMo₁2O₄0（VO）₂]和两种带帽Keggin型结构的杂多化合物:H₁1[PMo₁2O₄0（VO）₄][V₂O₇]₂·3H₂O、H₇[AsMo₈V₆O₄2]·en·4H₂O,并用X射线单晶衍射、IR光谱等手段进行了表征。 另外,本论文还研究了杂多化合物（NH₄）₇[Mo₈V₅O₄0]·10H₂O和（NH₄）₁5[Ce（Mo₉V₂O₃9）₂]·5H₂O在仲辛醇氧化制己酸中的催化性能,结果表明（NH₄）₇[Mo₈V₅O₄0]·10H₂O和（NH₄）15[Ce（Mo₉V₂o₃9）2]·5H₂O这两种杂多化合物均有较好的催化活性, 且（NH₄）₇[Mo₈V₅O₄0]·10H₂O优于（NH₄）₁5[Ce（Mo₉V₂O₃9）₂]·5H₂O。 以（NH₄）₇[Mo₈V₅O₄0]·10H₂O为催化剂的最佳反应条件为:反应温度100℃,反应时间11h,催化剂用量为仲辛醇质量的1.4%更多还原

【Abstract】 A series of charge-transfer complexes exhibiting photochromic properities were synthesized and charactered by X-ray crystallography, IR, UV, diffusion reflectance electronic spectra and ESR. The solid reflectance electronic spectra and IR indicate the presence of interaction between the heteropolyanion and the organic substrates in the solid state. Photosensitivity to ultraviolet light was assessed for the complexes, resulting in charge-transfer by oxidation of the organic substrates and the reduction of the heteropolyanion.Four novel polyoxometalate compounds containing transition metals: [(PW₁₂O₄₀){Zn(C₁₀H₈N₂)₂（H₂O）}]·1.5[Zn(C₁₀H₈N₂)₃]·2（OH^-）·H₂O（1）, [Zn(C₁₀H₈N₂)₃][PMo₁₂O₄₀（VO）₂] （2） , H₁₁[PMo₁₂O₄₀（VO）₄][V₂O₇]₂·3H₂O （3） and H₇[AsMo₈V₆O₄₂]·en·4H₂O （4） were synthesized and characterized by X-ray crystallography and IR. The results of IR and X-ray analysis show that there exists strong interaction between the polyoxometalate and organic donors in compound （1） and compound （2）. The heteropolyanion of compound （3） exhibits a tetracapped α-Keggin-type structure, while the heteropolyanion of compound （4） has a novel bicapped pseudo-Keggin structure.The oxidation of 2-octanol to hexanoic acid using （NH₄）₇[Mo₈V₅O₄₀]·10H₂O and （NH₄）₁₅[Ce(Mo₉V₂O₃₉)₂]·5H₂O as the catalyst were studied. The results showed that （NH₄）₇[Mo₈V₅O₄₀]·10H₂O and （NH₄）₁₅[CeCMo₉V₂O₃₉₂]·5H₂O can improve the yield of hexanoic acid, and （NH₄）₇[Mo₈V₅O₄₀]·10H₂O is superior to （NH₄）₁₅[Ce(Mo₉V₂O₃₉)₂]·5H₂O. The optimum reaction conditions were obtained with （NH₄）₇[Mo₈V₅O₄₀]·10H₂O as catalyst.更多还原