A new Wells–Dawson organic–inorganic hybrid polytungstate containing dimeric silver coordination complexes: (Hpy)₂[Ag₂(phen)₄]₂(P₂W₁₈O₆₂)

An attempt to incorporate Ag⁺ ions and some organic-reducing ingredients (e.g. pyridine) simultaneously into a polyoxometalate is a challenging task due to the high-standard reduction potential of Ag⁺ ions. By using a second organic ligand to coordinate Ag⁺ first, we prepared a new polytungstate, (Hpy)₂[Ag₂(phen)₄]₂(P₂W₁₈O₆₂) (<b>1</b>) (py = pyridine (C₅NH₅), phen = 1,10-phenanthroline (C₁₂N₂H₈)), which contains discrete inorganic polyanions ([P₂W₁₈O₆₂]^6–), protonated pyridine molecules, and [Ag₂(phen)₄]²⁺ dimers. The isolated inorganic polyanions cluster close to the planes of (1 0 0) and are bound together by pyridine molecules via hydrogen bonds to form layers parallel to (1 0 0) at (0, <i>y</i>, <i>z</i>) and (0.5, <i>y</i>, <i>z</i>). The [Ag₂(phen)₄]²⁺ dimers are located between successive layers of (1 0 0) and represent an uncommon feature that the hexagonal benzene rings of phen molecules are directly overlapped face to face. Our work opens a new way for synthesis of other Wells–Dawson organic–inorganic hybrid polytungstates by controlling reactant addition order.由于银离子（Ag⁺）具有较高的标准还原电位，将银离子与部分有机还原组分（如吡啶）同时引入多金属氧酸盐（polyoxometalate）中是一项极具挑战性的工作。本研究通过先利用第二有机配体与银离子配位的策略，成功合成了一种新型多钨酸盐（polytungstate）：(Hpy)₂[Ag₂(phen)₄]₂(P₂W₁₈O₆₂)（化合物<b>1</b>），其中py为吡啶（pyridine，C₅NH₅）、phen为1,10-菲咯啉（1,10-phenanthroline，C₁₂N₂H₈）。该化合物包含离散的无机多阴离子([P₂W₁₈O₆₂]⁶⁻)、质子化吡啶分子以及[Ag₂(phen)₄]²⁺二聚体。孤立的无机多阴离子簇贴近(1 0 0)晶面，并通过吡啶分子间的氢键相互结合，在(0, y, z)与(0.5, y, z)位置形成平行于(1 0 0)晶面的层状结构。[Ag₂(phen)₄]²⁺二聚体位于相邻(1 0 0)晶面层之间，其具有一个罕见的结构特征：菲咯啉分子上的六元苯环以面对面的方式直接堆叠。本工作为通过调控反应物添加顺序合成其他威尔斯-道森（Wells–Dawson）型有机-无机杂化多钨酸盐提供了全新思路。

搜集汇总

背景与挑战

背景概述

该数据集描述了一种新型Wells–Dawson有机-无机杂化多钨酸盐化合物(Hpy)2[Ag2(phen)4]2(P2W18O62)，其通过先使用第二有机配体与Ag+配位的方法合成，解决了Ag+离子高还原电位的挑战。该化合物包含离散的无机聚阴离子、质子化吡啶分子和[Ag2(phen)4]2+二聚体，其中二聚体表现出罕见的苯环面对面重叠特征，为合成类似杂化多钨酸盐提供了新途径。