Vanadium Polyoxoanions within Coordination Polymers Based on a Macrocyclic Nickel Complex: Structural Diversities and Single-Crystal to Single-Crystal Transformation

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• 作者：Guang-Chuan Ou ; Xian-You Yuan ; Zhi-Zhang Li ; Wen-Yi Li ; Fei Zeng ; Ji-Hua Deng and Di-Chang Zhong
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：July 2016
• 年：2016
• 卷：2016
• 期：21
• 页码：3500-3505
• 全文大小：1766K
• ISSN：1099-0682c

文摘

Five three-dimensional (3D) coordination polymers, {(NiL)[(NiL)(V₁₆O₄₂)]}_n·2nH₂O (1), [(NiL)₃(VO₃)₆]_n·5nH₂O (2), [(NiL)₃(V₆O₁₈)]_n·7nH₂O (3), [(NiL)₃(V₈O₂₃)]_n (4), and [(NiL)₄(V₁₀O₂₉)]_n (5), have been obtained by the reaction of the macrocyclic nickel complex [NiL](ClO₄)₂ (L = 1,4,8,11-tetraazacyclotetradecane) with NH₄VO₃ under different conditions. Single-crystal X-ray diffraction analyses revealed that the [VO₃]^– anion assumes diverse species and structures in these five coordination polymers, including the [V₁₆O₄₂]_n^4n– sheet, [V₆O₁₈]^6– ring, [VO₃]_n^n– chain, [VO₃]_n^n– sheet, and [V₁₀O₂₉]_n^8n– chain. The [V₁₆O₄₂]_n^4n– sheets, [V₆O₁₈]^6– rings, [VO₃]_n^n– chains, [VO₃]_n^n– sheets, and [V₁₀O₂₉]_n^8n– chains are linked together through [NiL]²⁺ bridges to form the 3D frameworks of 1–5. The single-crystal to single-crystal transformation between 2 and desolvated 2 was successfully realized. Electrochemical measurements indicate that 2 and 4 are potential catalysts for water splitting.