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dc.contributor.authorFranco, Carloses_ES
dc.contributor.authorLloveras, Vegaes_ES
dc.contributor.authorMas Torrent, Martaes_ES
dc.contributor.authorRovira, Concepcióes_ES
dc.contributor.authorVeciana, Jaumees_ES
dc.date.accessioned2018-05-03T10:46:05Z-
dc.date.available2018-05-03T10:46:05Z-
dc.date.issued2017-01-18-
dc.identifier.citationJournal of the American Chemical Society 139(2): 686-692 (2017)es_ES
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10261/164380-
dc.descriptionFranco, Carlos et al.es_ES
dc.description.abstractCharge transfer/transport in molecular wires over varying distances is a subject of great interest The feasible transport mechanisms have been generally accounted for on the basis of tunneling or superexchange charge transfer operating over small distances which progressively gives way to hopping transport over larger distances. The underlying molecular sequential steps that likely take place during hopping and the operative mechanism occurring at intermediate distances have received much less attention given the difficulty in assessing detailed molecular-level information. We describe here the operating mechanisms for unimolecular electron transfer/transport in the ground state of radical-anion mixed-valence derivatives occurring between their terminal perchlorotriphenylmethyl/ide groups through thiophene-vinylene oligomers that act as conjugated wires of increasing length up to 53 Å. The unique finding here is that the net transport of the electron in the larger molecular wires is initiated by an electron-hole dissociation intermediated by hole delocalization (conformationally assisted and thermally dependent) forming tran-sient mobile polaronic states in the bridge that terminate by an electron-hole recombination at the other wire extreme. On the con-trary for the shorter radical-anions our results suggest that a flickering resonance mechanism which is intermediate between hop-ping and superexchange is the operative one. We support these mechanistic interpretations by applying the pertinent biased kinetic models of the charge/spin exchange rates determined by electron paramagnetic resonance and by molecular structural level infor-mation obtained from UV-Vis and Raman spectroscopies and by quantum chemical modelling.es_ES
dc.description.sponsorshipWe acknowledge the financial support from the Spanish MINECO/FEDER (grants CTQ2013-40480-R, CTQ2016- 7989-R, and CTQ2015-64618-R), Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Programme for Centres of Excellence in R&D (grant SEV2015-0496), the Generalitat de Catalunya (grants 2014SGR-17, 2014SGR-97, and XRQTC). We also acknowledge supercomputing resources provided by the Red Españ ola de Supercomputacion and the Networking Research Center of Bioengineering, Biomaterials and Nanomedicine (CIBERBBN). The work carried out at the University of Malaga was supported by MINECO/FEDER through the reference projects CTQ2012-33733 andCTQ2015-69391-P. The “Servicios Centrales de Apoyo a la Investigacioń ” of the University of Malaga are also acknowledged by generous access to its facilities. I.A. acknowledges the Spanish Ministerio de Educacion Cultura y Deporte for a FPU PhD scholarship.es_ES
dc.language.isoenges_ES
dc.publisherAmerican Chemical Societyes_ES
dc.relationMINECO/ICTI2013-2016/CTQ2013-40480-Res_ES
dc.relationMINECO/ICTI2013-2016/CTQ2016- 7989-Res_ES
dc.relationMINECO/ICTI2013-2016/CTQ2015-64618-Res_ES
dc.relationMINECO/ICTI2013-2016/SEV-2015-0496es_ES
dc.relationMINECO/ICTI2013-2016/CTQ2012-33733es_ES
dc.relationMINECO/ICTI2013-2016/CTQ2015-69391-Pes_ES
dc.relation.isversionofPostprintes_ES
dc.rightsopenAccesses_ES
dc.subjectIntramolecular electron-transferes_ES
dc.subjectThienylenevinylene oligomerses_ES
dc.subjectLength dependencees_ES
dc.subjectConductancees_ES
dc.titleOperative Mechanism of Hole-Assisted Negative Charge Motion in Ground States of Radical-Anion Molecular Wireses_ES
dc.typeartículoes_ES
dc.description.peerreviewedPeer reviewedes_ES
dc.relation.publisherversionhttp://dx.doi.org/10.1021/jacs.6b08649es_ES
dc.contributor.funderMinisterio de Economía y Competitividad (España)es_ES
dc.contributor.funderGeneralitat de Catalunyaes_ES
dc.contributor.funderCentro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)es_ES
dc.relation.csices_ES
oprm.item.hasRevisionno ko 0 false*
dc.identifier.funderhttp://dx.doi.org/10.13039/501100005053es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100002809es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100003329es_ES
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