Johannes Beck, Thomas Bredow, Jörg Daniels, Marcus Zink, Doris Ernsthäuser, Dominik Thönnes
{"title":"Coordination Networks from [Te4]2+ Clusters and Polynitriles","authors":"Johannes Beck, Thomas Bredow, Jörg Daniels, Marcus Zink, Doris Ernsthäuser, Dominik Thönnes","doi":"10.1002/zaac.202400112","DOIUrl":null,"url":null,"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.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Zeitschrift für anorganische und allgemeine Chemie","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/zaac.202400112","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
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.