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Mixed valence radic...
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Christensen, M. A.Köpenhamns universitet,University of Copenhagen
(författare)
Mixed valence radical cations and intermolecular complexes derived from indenofluorene-extended tetrathiafulvalenes
- Artikel/kapitelEngelska2014
Förlag, utgivningsår, omfång ...
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2014-10-20
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Royal Society of Chemistry (RSC),2014
Nummerbeteckningar
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LIBRIS-ID:oai:research.chalmers.se:8acf1c89-b996-4db5-a357-ca087a838804
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https://research.chalmers.se/publication/209566URI
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https://doi.org/10.1039/c4tc02178aDOI
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Språk:engelska
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Sammanfattning på:engelska
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Ämneskategori:art swepub-publicationtype
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Ämneskategori:ref swepub-contenttype
Anmärkningar
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Engineering of mixed-valence (MV) radical cations and intermolecular complexes based on pi-extended tetrathiafulvalenes (TTFs) is central for the development of organic conductors. On another front, redox-controlled dimerization of radical cations has recently been recognized as an important tool in supramolecular chemistry. Here we show that pi-extended TTFs based on the indenofluorene core, prepared by Horner-Wadsworth-Emmons reactions, undergo reversible and stepwise one-electron oxidations and that the detectable, intermediate radical cation forms remarkably strong intermolecular MV ([neutral.cation]) and pi-dimer ([cation.cation]) complexes with near-infrared radical cation absorptions. The radical cation itself seems to be a so-called Class III MV species in the Robin-Day classification. The formation of MV dimers was corroborated by ESR spectroelectrochemical studies, revealing two slightly different ESR signals upon oxidation, one assigned to the MV dimer and the other to the cation monomer. Crystals of the radical cation with different anions (PF6- , BF4-, and TaF6-) were grown by electrocrystallization. Conductance studies revealed that the salts behave as semiconductors with the hexafluorotantalate salt exhibiting the highest conductance. Using a custom-built ESR spectrometer with sub-femtomole sensitivity, the magnetic properties of one crystal were investigated. While the spin-to-spin interaction between radical cations was negligible, a high cooperativity coupling to the microwave field was observed - as a result of an exceptionally narrow spin line width and high spin density. This could have great potential for applications in quantum computation where crystalline spin ensembles are exploited for their long coherence times.
Ämnesord och genrebeteckningar
Biuppslag (personer, institutioner, konferenser, titlar ...)
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Parker, C. R.Köpenhamns universitet,University of Copenhagen
(författare)
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Sorensen, T. J.Köpenhamns universitet,University of Copenhagen
(författare)
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de Graaf, Sebastian Erik,1986Chalmers tekniska högskola,Chalmers University of Technology(Swepub:cth)degraaf
(författare)
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Morsing, T. J.Köpenhamns universitet,University of Copenhagen
(författare)
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Brock-Nannestad, T.Köpenhamns universitet,University of Copenhagen
(författare)
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Bendix, J.Köpenhamns universitet,University of Copenhagen
(författare)
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Haley, M. M.University of Oregon
(författare)
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Rapta, P.Slovak University of Technology Bratislava
(författare)
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Danilov, Andrey,1961Chalmers tekniska högskola,Chalmers University of Technology(Swepub:cth)danilov
(författare)
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Kubatkin, Sergey,1959Chalmers tekniska högskola,Chalmers University of Technology(Swepub:cth)kubatkin
(författare)
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Hammerich, O.Köpenhamns universitet,University of Copenhagen
(författare)
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Nielsen, M. B.Köpenhamns universitet,University of Copenhagen
(författare)
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Köpenhamns universitetChalmers tekniska högskola
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Journal of Materials Chemistry C: Royal Society of Chemistry (RSC)2:48, s. 10428-104382050-75342050-7526
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Christensen, M. ...
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Parker, C. R.
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Sorensen, T. J.
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de Graaf, Sebast ...
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Morsing, T. J.
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Brock-Nannestad, ...
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visa fler...
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Bendix, J.
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Haley, M. M.
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Rapta, P.
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Danilov, Andrey, ...
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Kubatkin, Sergey ...
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Hammerich, O.
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Nielsen, M. B.
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