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Tetrahalidocuprates(II) – structure and EPR spectroscopy

  • We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principalWe present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.show moreshow less

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Metadaten
Author:Alette Winter, Kerstin Thiel, André Zabel, Tillmann Klamroth, Andreas Pöppl, Alexandra Kelling, Uwe SchildeORCiDGND, Andreas TaubertORCiDGND, Peter Strauch
URN:urn:nbn:de:kobv:517-opus4-95012
Subtitle (English):Part 2: tetrachloridocuprates(II)
Series (Serial Number):Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe (240)
Document Type:Postprint
Language:English
Date of first Publication:2013/11/29
Year of Completion:2013
Publishing Institution:Universität Potsdam
Release Date:2016/09/06
Tag:copper(II) halide salts; electron-spin resonance; ionic liquid; liquid-crystal precursors; magnetic-properties; molecular-structure; paramagnetic-resonance; square planar; temperature phase; tetrachlorocuprate(II) salts
First Page:1019
Last Page:1030
Source:New J. Chem. (2014) Nr. 38, S. 1019-1030. - DOI: 10.1039/C3NJ01039B
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Peer Review:Referiert
Publication Way:Open Access
Licence (German):License LogoKeine Nutzungslizenz vergeben - es gilt das deutsche Urheberrecht