Efficient Synthesis of Ir-Polyoxometalate Cluster Using a Continuous Flow Apparatus and STM Investigation of Its Coassembly Behavior on HOPG Surface

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• 作者：Junyong Zhang ; Shaoqing Chang ; Bryan H. R. Suryanto ; Chunhua Gong ; Xianghua Zeng ; Chuan Zhao ; Qingdao Zeng ; Jingli Xie
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5585-5591
• 全文大小：497K
• 年卷期：0
• ISSN：1520-510X

文摘

Taking advantage of a continuous-flow apparatus, the iridium(III)-containing polytungstate cluster K₁₂Na₂H₂[Ir₂Cl₈P₂W₂₀O₇₂]·37H₂O (1) was obtained in a reasonable yield (13% based on IrCl₃·H₂O). Compound 1 was characterized by Fourier transform IR, UV–visible, ³¹P NMR, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis measurements. ³¹P NMR, ESI-MS, and elemental analysis all indicated 1 was a new polytungstate cluster compared with the reported K₁₄[(IrCl₄)KP₂W₂₀O₇₂] compound. Intriguingly, the successful isolation of 1 relied on the custom-built flow apparatus, demonstrating the uniqueness of continuous-flow chemistry to achieve crystalline materials. The catalytic properties of 1 were assessed by investigating the activity on catalyzing the electro-oxidation of ruthenium tris-2,2′-bipyridine [Ru(bpy)₃]^2+/3+. The voltammetric behavior suggested a coupled catalytic behavior between [Ru(bpy)₃]^3+/2+ and 1. Furthermore, on the highly oriented pyrolytic graphite surface, 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) was used as the two-dimensional host network to coassemble cluster 1; the surface morphology was observed by scanning tunneling microscope technique. “S”-shape of 1 was observed, indicating that the cluster could be accommodated in the cavity formed by two TCDB host molecules, leading to a TCDB/cluster binary structure.