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dc.contributor.authorNärhi, Sari
dc.contributor.authorKutuniva, Johanna
dc.contributor.authorLajunen, Marja
dc.contributor.authorLahtinen, Manu
dc.contributor.authorTuononen, Heikki
dc.contributor.authorKarttunen, Antti
dc.contributor.authorOilunkaniemi, Raija
dc.contributor.authorLaitinen, Risto
dc.date.accessioned2015-11-30T09:35:44Z
dc.date.available2015-11-30T09:35:44Z
dc.date.issued2014
dc.identifier.citationNärhi, S., Kutuniva, J., Lajunen, M., Lahtinen, M., Tuononen, H., Karttunen, A., Oilunkaniemi, R., & Laitinen, R. (2014). Identification of mixed bromidochloridotellurate anions in disordered crystal structures of (bdmim)2[TeX2Y4] (X, Y = Br, Cl; bdmim = 1-butyl-2,3-dimethylimidazolium) by combined application of Raman spectroscopy and solid-state DFT calculations. <i>Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy</i>, <i>117</i>, 728-738. <a href="https://doi.org/10.1016/j.saa.2013.09.063" target="_blank">https://doi.org/10.1016/j.saa.2013.09.063</a>
dc.identifier.otherCONVID_22811315
dc.identifier.otherTUTKAID_57748
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47857
dc.description.abstractThe discrete mixed [TeBrxCl6−x]2− anions in their disordered crystal structures have been identified by using the phases prepared by the reaction of 1-butyl-2,3-dimethylimidazolium halogenides (bdmim)X with tellurium tetrahalogenides TeX4 (X = Cl, Br) as examples. Homoleptic (bdmim)2[TeX6] [X = Cl (1), Br (2)] and mixed (bdmim)2[TeBr2Cl4] (3), and (bdmim)2[TeBr4Cl2] (4) are formed depending on the choice of the reagents, and their crystal structures have been determined by single-crystal X-ray diffraction. The coordination environments of tellurium in all hexahalogenidotellurates are almost octahedral. Because of the crystallographic disorder, the mixed [TeBr2Cl4]2− and [TeBr4Cl2]2− anions in 3 and 4 cannot be identified in their crystal structures. Pawley refinement of the X-ray powder diffraction patterns of 1–4 indicates the presence of single phases in all four products. The solid state Raman spectra of 1–4 were assigned with help of DFT calculations that were performed both for the discrete anions in vacuum and for the complete crystal structures employing periodic boundary conditions. The fundamental vibrations of the homoleptic [TeX6]2− (X = Cl, Br) anions could be well reproduced by the solid-state DFT computations and enabled a complete assignment of the Raman spectra. While the presence of cis-isomers in both [TeBr2Cl4]2− and [TeBr4Cl2]2− could be inferred by the computed fundamental vibrations, that of trans-isomers among the reaction products is, however, also possible. The pathway of the formation of [TeX4Y2]2− isomers from TeX4 and Y− (X, Y = Cl, Br) was also explored by DFT calculations both in vacuum and in solution and indicated that both reactions afforded 80 mol% of cis-isomers and 20 mol% of trans-isomers.
dc.language.isoeng
dc.publisherElsevier B.V.
dc.relation.ispartofseriesSpectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
dc.subject.otherbromidikloriditelluraatit
dc.subject.otherkiinteän tilan DFT laskut
dc.subject.otherRaman-spektroskopia
dc.subject.otherkristallografia
dc.subject.otherbromidochloridotellurates
dc.subject.othersolid-state DFT calculations
dc.subject.otherRaman spectroscopy
dc.titleIdentification of mixed bromidochloridotellurate anions in disordered crystal structures of (bdmim)2[TeX2Y4] (X, Y = Br, Cl; bdmim = 1-butyl-2,3-dimethylimidazolium) by combined application of Raman spectroscopy and solid-state DFT calculations
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511253812
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-25T13:15:08Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange728-738
dc.relation.issn1386-1425
dc.relation.numberinseries0
dc.relation.volume117
dc.type.versionacceptedVersion
dc.rights.copyright© 2013 Elsevier B.V. This is a final draft version of an article whose final and definitive form has been published by Elsevier. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.subject.ysokidetiede
jyx.subject.urihttp://www.yso.fi/onto/yso/p643
dc.relation.doi10.1016/j.saa.2013.09.063
dc.type.okmA1


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