Two Novel One-Dimensional α-Keggin-Based Coordination Polymers with Argentophilic {Ag3}3+/{Ag4}4+ Clusters

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• 作者：Limei Dai ; Wansheng You ; Enbo Wang ; Shuixing Wu ; Zhongmin Su ; Qinghua Du ; Yi Zhao ; Yong Fang
• 刊名：Crystal Growth & Design
• 出版年：2009
• 出版时间：May 6, 2009
• 年：2009
• 卷：9
• 期：5
• 页码：2110-2116
• 全文大小：412K
• 年卷期：v.9,no.5(May 6, 2009)
• ISSN：1528-7505

文摘

Two novel α-Keggin anion-based coordination polymers with argentophilic {Ag₃}³⁺/{Ag₄}⁴⁺ clusters, [{Ag₃(bpy)₄}{PMo₁₂O₄₀}]·2H₂O (1), [{Ag(bpy)}₂{Ag₄(bpy)₆}{PMo₁₁VO₄₀}][{Ag(bpy)}₂{PMo₁₁VO₄₀}] (2), have been hydrothemally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The crystal data for these are the following: C₄₀H₃₆Ag₃Mo₁₂N₈O₄₂P (1), triclinic P, a = 10.5245(19) Å, b = 12.058(2) Å, c = 13.530(2) Å, α = 87.015(2)°, β = 72.146(2)°, γ = 86.563(2)°, Z = 1; C₁₀₀H₈₀Ag₈Mo₂₂N₂₀O₈₀P₂V₂ (2), triclinic P, a = 13.3603(15) Å, b = 16.3035(18) Å, c = 16.7523(19) Å, α = 89.896(2)°, β = 84.000(2)°, γ = 88.066(2)°, Z = 1. Polymer 1 consists of an infinite zigzag one-dimensional (1D) chain constructed from [Ag₃(bpy)₄]³⁺ clusters and [PMo₁₂O₄₀]³⁻ anions. Polymer 2 consists of isolated bisupporting [{Ag(bpy)}₂{PMo₁₁VO₄₀}]²⁻ anions and infinite 1D cationic chains [{Ag(bpy)}₂{Ag₄(bpy)₆}{PMo₁₁VO₄₀}]²⁺ constructed from [{Ag(bpy)}₂{PMo₁₁VO₄₀}]²⁻ anions bridged via {Ag₄(bpy)₆}⁴⁺ clusters. Argentophilic {Ag₃}³⁺ and {Ag₄}⁴⁺ interactions exist in polymers 1 and 2. Ag···Ag interactions were proven using density functional theory, and the luminescent properties were investigated in polymers 1 and 2. The electrochemical behavior of the polymers modified carbon paste electrode (1-CPE, 2-CPE) and their electrocatalytic reductions of nitrite were investigated. Both 1-CPE and 2-CPE show good electrocatalytic activity toward the reduction of the nitrite and remarkable stability that can be ascribed to their insolubility.