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2017-02-22Zeitschriftenartikel DOI: 10.18452/18444
Light-Controlled Reversible Modulation of Frontier Molecular Orbital Energy Levels in Trifluoromethylated Diarylethenes
dc.contributor.authorHerder, Martin
dc.contributor.authorEisenreich, Fabian
dc.contributor.authorBonasera, Aurelio
dc.contributor.authorGrafl, Anna
dc.contributor.authorGrubert, Lutz
dc.contributor.authorPätzel, Michael
dc.contributor.authorSchwarz, Jutta
dc.contributor.authorHecht, Stefan
dc.date.accessioned2017-10-09T11:11:13Z
dc.date.available2017-10-09T11:11:13Z
dc.date.issued2017-02-22
dc.identifier.urihttp://edoc.hu-berlin.de/18452/19123
dc.description.abstractAmong bistable photochromic molecules, diarylethenes (DAEs) possess the distinct feature that upon photoisomerization they undergo a large modulation of their π-electronic system, accompanied by a marked shift of the HOMO/LUMO energies and hence oxidation/reduction potentials. The electronic modulation can be utilized to remote-control charge- as well as energy-transfer processes and it can be transduced to functional entities adjacent to the DAE core, thereby regulating their properties. In order to exploit such photoswitchable systems it is important to precisely adjust the absolute position of their HOMO and LUMO levels and to maximize the extent of the photoinduced shifts of these energy levels. Here, we present a comprehensive study detailing how variation of the substitution pattern of DAE compounds, in particular using strongly electron-accepting and chemically stable trifluoromethyl groups either in the periphery or at the reactive carbon atoms, allows for the precise tuning of frontier molecular orbital levels over a broad energy range and the generation of photoinduced shifts of more than 1 eV. Furthermore, the effect of different DAE architectures on the transduction of these shifts to an adjacent functional group is discussed. Whereas substitution in the periphery of the DAE motif has only minor implications on the photochemistry, trifluoromethylation at the reactive carbon atoms strongly disturbs the isomerization efficiency. However, this can be overcome by using a nonsymmetrical substitution pattern or by combination with donor groups, rendering the resulting photoswitches attractive candidates for the construction of remote-controlled functional systems.eng
dc.language.isoeng
dc.publisherHumboldt-Universität zu Berlin
dc.subjectcyclic voltammetryeng
dc.subjectdiaryletheneseng
dc.subjectfrontier molecular orbital energieseng
dc.subjectphotochromismeng
dc.subjectquantum yieldseng
dc.subject.ddc540 Chemie und zugeordnete Wissenschaften
dc.titleLight-Controlled Reversible Modulation of Frontier Molecular Orbital Energy Levels in Trifluoromethylated Diarylethenes
dc.typearticle
dc.identifier.urnurn:nbn:de:kobv:11-110-18452/19123-3
dc.identifier.doihttp://dx.doi.org/10.18452/18444
local.edoc.pages12
local.edoc.type-nameZeitschriftenartikel
local.edoc.institutionMathematisch-Naturwissenschaftliche Fakultät
dc.description.versionPeer Reviewed

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