Coordination Networks from [Te4]2+ Clusters and Polynitriles

Johannes Beck, Thomas Bredow, Jörg Daniels, Marcus Zink, Doris Ernsthäuser, Dominik Thönnes
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Abstract

The reactions of a series of organic polynitriles with [Te4][AsF6]2 in liquid SO2 solution lead either to reduction of [Te4]2+ to elemental tellurium or to the formation of coordination polymers. With 1,3‐dicyanobenzene (1,3‐DCB), 1,4‐dicyanobenzene (1,4‐DCB), 1,2,4,5‐tetracyanobenzene (TCB), tetracyanoethylene (TCNE) and tetracyanochinodimethane (TCNQ) the coordination complexes [Te4][AsF6]2 · 2(1,3‐DCB), [Te4][AsF6]2 · 3(1,4‐DCB) · 2SO2, [Te4][AsF6]2 · TCB, [Te4][AsF6]2 · TCNE and [Te4][AsF6]2 · TCNQ · 8SO2 were isolated and characterized by crystal structure analyses and vibrational Raman spectroscopy. The nitriles are coordinated to the square‐planar clusters forming 1D chains, 2D arrangements and 3D networks. Tetrakis(dicyanomethylene)‐cyclobutendiide [C4(C{CN}2)4]2‒ is oxidized by [Te4]2+ to the neutral cyanocarbon C4(C{CN}2)4 structurally representing a 4[radialene]. The ionization potentials and electron affinities of the cyanamide anion, cyanogen, 1,2‐DCB, 1,3‐DCB, 1,4‐DCB, TCB, C4(C{CN}2)4, TCNE and TCNQ and those polynitriles, which cause reduction of [Te4]2+, were calculated at coupled‐cluster level of theory in order to examine possible reasons for the stability of the coordination polymers based on electronic properties of the nitriles.
来自 [Te4]2+ 簇和多腈的配位网络
在液态二氧化硫溶液中,一系列有机多腈与[Te4][AsF6]2的反应要么导致[Te4]2+还原为元素碲,要么形成配位聚合物。在 1,3-Dicyanobenzene (1,3-DCB)、1,4-dicyanobenzene (1,4-DCB)、1,2,4,5-tetracyanobenzene (TCB)、tetracyanoethylene (TCNE) 和 tetracyanochinodimethane (TCNQ) 的作用下,[Te4][AsF6]2 - 2(1、3-DCB)、[Te4][AsF6]2 - 3(1,4-DCB)- 2SO2、[Te4][AsF6]2 - TCB、[Te4][AsF6]2 - TCNE 和 [Te4][AsF6]2 - TCNQ - 8SO2 配位复合物,并通过晶体结构分析和振动拉曼光谱对其进行了表征。腈类配位到方形平面簇上,形成一维链、二维排列和三维网络。四(二氰基亚甲基)环丁二烯[C4(C{CN}2)4]2-被[Te4]2+氧化成中性氰碳 C4(C{CN}2)4,其结构代表 4[辐射烯]。在耦合簇理论水平上计算了氰酰胺阴离子、氰原、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、TCB、C4(C{CN}2)4、TCNE 和 TCNQ 以及那些导致 [Te4]2+ 还原的多腈的电离电位和电子亲和性,以便根据腈的电子特性研究配位聚合物稳定性的可能原因。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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