Structural and Spectral Characterization of Two Charge-Transfer Salts Formed by Ferrocenyl and Polyoxometalate Units

详细信息    查看全文

• 作者：Haisheng Xu ; Lei Zhang ; Zuoxi Li ; Zhanfeng Li ; Huaiming Hu and Ganglin Xue
• 关键词：Charge ; transfer ; Polyoxometalates ; Ferrocene ; Structure characterization
• 刊名：Journal of Cluster Science
• 出版年：2010
• 出版时间：June, 2010
• 年：2010
• 卷：21
• 期：2
• 页码：211-221
• 全文大小：467.0 KB

文摘

Two charge-transfer (CT) salts based on the ferrocenyl cation CpFeCpCH₂N+(CH₃)₃ and Keggin-type anion [PW₁₂O₄₀]3− or [SiMo₁₂O₄₀]4− with the ratio of ferrocenyl:polyanion of 3:1 or 4:1, [CpFeCpCH₂N(CH₃)₃]₃[PW₁₂O₄₀] (1) and [CpFeCp-CH₂N+(CH₃)₃]₄[SiMo₁₂O₄₀] (2), were synthesized in high yields (68–71 % ) by traditional solution synthetic method and their structures were determined by X-ray diffraction analysis. The two salts both crystallize in triclinic space group P[`1] P\overline{1} and show the close interaction of the cyclopentadienyl ligand with the surface of the polyoxometalate. The UV–Vis diffuse reflectance spectra of 1 and 2 in the solid state indicate the presence of a new absorption band at λ _max = 550 and 630 nm, respectively, attributed to charge-transfer transitions between the ferrocenyl donors and the POM acceptors. The large difference of the shapes and positions of fluorescence emission bands of salts from the start materials also suggested the occurrence of a charge transfer process between the ferrocenyl cation and polyanion.