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231224s2017 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.24798
|2 doi
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|a pubmed24n0902.xml
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|a (NLM)28394037
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|a DE-627
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|c DE-627
|e rakwb
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|a eng
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|a Witte, Matthias
|e verfasserin
|4 aut
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|a Cu6 (NGuaS)6 ]2+ and its oxidized and reduced derivatives
|b Confining electrons on a torus
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|c 2017
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|a Text
|b txt
|2 rdacontent
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|a ƒaComputermedien
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|2 rdamedia
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|a ƒa Online-Ressource
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|a Date Revised 20.11.2019
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a © 2017 Wiley Periodicals, Inc.
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|a The hexanuclear thioguanidine mixed-valent copper complex cation [Cu6 (NGuaS)6 ]+2 (NGuaS = o-SC6 H4 NC(NMe2 )2 ) and its oxidized/reduced states are theoretically analyzed by means of density functional theory (DFT) (TPSSh + D3BJ/def2-TZV (p)). A detailed bonding analysis using overlap populations is performed. We find that a delocalized Cu-based ring orbital serves as an acceptor for donated S p electrons. The formed fully delocalized orbitals give rise to a confined electron cloud within the Cu6 S6 cage which becomes larger on reduction. The resulting strong electrostatic repulsion might prevent the fully reduced state. Experimental UV/Vis spectra are explained using time-dependent density functional theory (TD-DFT) and analyzed with a natural transition orbital analysis. The spectra are dominated by MLCTs within the Cu6 S6 core over a wide range but LMCTs are also found. The experimental redshift of the reduced low energy absorption band can be explained by the clustering of the frontier orbitals. © 2017 Wiley Periodicals, Inc
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a charge decomposition analysis
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|a copper thiolate complexes
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|a density functional theory
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|a time-dependent-DFT
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|a Rohrmüller, Martin
|e verfasserin
|4 aut
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|a Gerstmann, Uwe
|e verfasserin
|4 aut
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| 700 |
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|a Henkel, Gerald
|e verfasserin
|4 aut
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|a Schmidt, Wolf Gero
|e verfasserin
|4 aut
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|a Herres-Pawlis, Sonja
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 38(2017), 20 vom: 15. Juli, Seite 1752-1761
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:38
|g year:2017
|g number:20
|g day:15
|g month:07
|g pages:1752-1761
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|u http://dx.doi.org/10.1002/jcc.24798
|3 Volltext
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