Solid-Gas Phase Synthesis of Coordination Networks by Using Redox‐Active Ligands and Elucidation of Their Oxidation Reaction
Solid-Gas Phase Synthesis of Coordination Networks by Using Redox‐Active Ligands and Elucidation of Their Oxidation Reaction
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使用氧化还原活性配体固-气相合成配位网络及其氧化反应的阐明
DOI：
10.1002/chem.201902105
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Kawano Masaki
中科院分区：
文献类型：
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作者：
Den Taizen;Usov Pavel M.;Kim Jaejun;Hashizume Daisuke;Ohtsu Hiroyoshi;Kawano Masaki
协调网络的形成是一个受多种因素影响的复杂过程。已经开发了许多合成策略，试图控制这些因素并指导最终产品的结构。然而，配位键的形成和结构组装过程通常要么在溶液中发生，要么在固态中发生。相比之下，气相网络合成在很大程度上仍未被探索。其中，由氧化还原活性的2，5，8-三(4-吡啶基)-1，3-二氮杂菲(HTPDAP)配体与ZnX2(X=I，Br)之间的固气相反应得到了两个新的二维配位网络。通过从头算粉末X-射线衍射分析确定了它们的结构，并表征了一个新的卤化锌三聚体簇合物。这一策略与传统的溶剂热合成方法不同，后者导致了一维配位聚合物的合成。通过固态循环伏安法研究了这些材料的本征电活性，揭示了HTPDAP和基于卤化物的过程的存在。用NOPF6试剂对二维网络进行化学氧化，意外地形成了HTPDAP的硝化类似物，即二质子化4，6，7，9‐tetranitro‐2，5，8‐tris(4‐pyridyl)diazaphenalene阳离子的PF6−盐(记为N-TPDAP)，并对其进行了分离和表征。这些结果为含HTPDAP网络的氧化过程提供了更深入的见解，并揭示了独特的氧化还原诱导的化学转化。
Formation of coordination networks is a complex process affected by a multitude of factors. Many synthetic strategies have been developed that attempt to control these factors and direct the structure of the final product. Coordination bond formation and structural assembly processes, however, typically take place either in the solution or solid states. In comparison, gas‐phase network synthesis remains largely unexplored. Herein, two new two‐dimensional coordination networks are obtained from the solid–gas phase reaction between ZnX2(X=I, Br) and the redox‐active 2,5,8‐tri(4‐pyridyl)1,3‐diazaphenalene (HTPDAP) ligand. Their structures were solved by ab initio powder X‐ray diffraction analysis and feature a novel Zn halide trimeric cluster. This strategy is contrasted with a conventional solvothermal synthesis, which led to a one‐dimensional coordination polymer instead. The intrinsic electroactive properties of these materials were probed by solid‐state cyclic voltammetry measurements, which revealed the presence of HTPDAP and halide‐based processes. Chemical oxidation of the two‐dimensional networks by using NOPF6agent, unexpectedly, led to the formation of a nitrated analog of HTPDAP, the PF6−salt of diprotonated 4,6,7,9‐tetranitro‐2,5,8‐tris(4‐pyridyl)diazaphenalene cation (denotedN‐TPDAP), which was isolated and characterized. These results provide deeper insights into the oxidation process of HTPDAP‐containing networks and uncover unique redox‐induced chemical transformations.