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DC Field	Value	Language
dc.contributor.author	Franco, Carlos	es_ES
dc.contributor.author	Lloveras, Vega	es_ES
dc.contributor.author	Mas Torrent, Marta	es_ES
dc.contributor.author	Rovira, Concepció	es_ES
dc.contributor.author	Veciana, Jaume	es_ES
dc.date.accessioned	2018-05-03T10:46:05Z	-
dc.date.available	2018-05-03T10:46:05Z	-
dc.date.issued	2017-01-18	-
dc.identifier.citation	Journal of the American Chemical Society 139(2): 686-692 (2017)	es_ES
dc.identifier.issn	0002-7863	-
dc.identifier.uri	http://hdl.handle.net/10261/164380	-
dc.description	Franco, Carlos et al.	es_ES
dc.description.abstract	Charge 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.sponsorship	We 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.iso	eng	es_ES
dc.publisher	American Chemical Society	es_ES
dc.relation	MINECO/ICTI2013-2016/CTQ2013-40480-R	es_ES
dc.relation	MINECO/ICTI2013-2016/CTQ2016- 7989-R	es_ES
dc.relation	MINECO/ICTI2013-2016/CTQ2015-64618-R	es_ES
dc.relation	MINECO/ICTI2013-2016/SEV-2015-0496	es_ES
dc.relation	MINECO/ICTI2013-2016/CTQ2012-33733	es_ES
dc.relation	MINECO/ICTI2013-2016/CTQ2015-69391-P	es_ES
dc.relation.isversionof	Postprint	es_ES
dc.rights	openAccess	es_ES
dc.subject	Intramolecular electron-transfer	es_ES
dc.subject	Thienylenevinylene oligomers	es_ES
dc.subject	Length dependence	es_ES
dc.subject	Conductance	es_ES
dc.title	Operative Mechanism of Hole-Assisted Negative Charge Motion in Ground States of Radical-Anion Molecular Wires	es_ES
dc.type	artículo	es_ES
dc.description.peerreviewed	Peer reviewed	es_ES
dc.relation.publisherversion	http://dx.doi.org/10.1021/jacs.6b08649	es_ES
dc.contributor.funder	Ministerio de Economía y Competitividad (España)	es_ES
dc.contributor.funder	Generalitat de Catalunya	es_ES
dc.contributor.funder	Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)	es_ES
dc.relation.csic	Sí	es_ES
oprm.item.hasRevision	no ko 0 false	*
dc.identifier.funder	http://dx.doi.org/10.13039/501100005053	es_ES
dc.identifier.funder	http://dx.doi.org/10.13039/501100002809	es_ES
dc.identifier.funder	http://dx.doi.org/10.13039/501100003329	es_ES
Appears in Collections:	(ICMAB) Artículos