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Steric-shielding vs sigma-pi orbital interactions in triplet-triplet energy transfer

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Steric-shielding vs sigma-pi orbital interactions in triplet-triplet energy transfer

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dc.contributor.author Andreu Ros, María Inmaculada es_ES
dc.contributor.author Morera Bertomeu, Isabel María es_ES
dc.contributor.author Palumbo, Fabrizio es_ES
dc.contributor.author Sastre Navarro, German Ignacio es_ES
dc.contributor.author Bosca Mayans, Francisco es_ES
dc.contributor.author Miranda Alonso, Miguel Ángel es_ES
dc.date.accessioned 2016-05-26T10:43:45Z
dc.date.available 2016-05-26T10:43:45Z
dc.date.issued 2015
dc.identifier.issn 2041-6520
dc.identifier.uri http://hdl.handle.net/10251/64783
dc.description.abstract he influence of non-covalent σ–π orbital interactions on triplet–triplet energy transfer (TTET) through tuning of the donor excitation energy remains basically unexplored. In the present work, we have investigated intermolecular TTET using donor moieties covalently linked to a rigid cholesterol (Ch) scaffold. For this purpose, diaryl ketones of π,π* electronic configuration tethered to α- or β-Ch were prepared from tiaprofenic acid (TPA) and suprofen (SUP). The obtained systems TPA-α-Ch, TPA-β-Ch, SUP-α-Ch and SUP-β-Ch were submitted to photophysical studies (laser flash photolysis and phosphorescence), in order to delineate the influence of steric shielding and σ–π orbital interactions on the rate of TTET to a series of energy acceptors. As a matter of fact, fine tuning of the donor triplet energy significantly modifies the rate constants of TTET in the absence of diffusion control. The experimental results are rationalized by means of theoretical calculations using first principles methods based on DFT as well as molecular dynamics. es_ES
dc.description.sponsorship Financial support from the Generalitat Valenciana (Prometeo Program), the Spanish Government (CTQ2010-19909, SEV-2012-0267 and FPU fellowship for F.P.) and the Carlos III Institute of Health (Grant RIRAAF, RETICS program and Miguel Servet Contract CP11/00154 for I. A.) is gratefully acknowledged. We thank ASIC-UPV for computing time. Dedicated to Prof. Diego Cortes on the occasion of his 60th birthday. en_EN
dc.language Inglés es_ES
dc.publisher Royal Society of Chemistry: Chemical Science es_ES
dc.relation.ispartof Chemical Science es_ES
dc.rights Reconocimiento (by) es_ES
dc.subject DENSITY FUNCTIONALS es_ES
dc.subject MOLECULAR-DYNAMICS es_ES
dc.subject PULSE-RADIOLYSIS es_ES
dc.subject SYSTEMS es_ES
dc.subject STATE es_ES
dc.subject ABSORPTION es_ES
dc.subject SIMULATION es_ES
dc.subject SPECTRA es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.title Steric-shielding vs sigma-pi orbital interactions in triplet-triplet energy transfer es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1039/c5sc00823a
dc.relation.projectID info:eu-repo/grantAgreement/MICINN//CTQ2010-19909/ES/MECANISMOS IMPLICADOS EN LA FOTO-REACTIVIDAD ENTRE FARMACOS CON PROPIEDADES ANTINEOPLASICAS Y SUS BIOMOLECULAS DIANA/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MICINN//CP11%2F00154/ES/CP11%2F00154/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Química - Departament de Química es_ES
dc.description.bibliographicCitation Andreu Ros, MI.; Morera Bertomeu, IM.; Palumbo, F.; Sastre Navarro, GI.; Bosca Mayans, F.; Miranda Alonso, MÁ. (2015). Steric-shielding vs sigma-pi orbital interactions in triplet-triplet energy transfer. Chemical Science. 6(7):4035-4041. https://doi.org/10.1039/c5sc00823a es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://dx.doi.org/10.1039/c5sc00823a es_ES
dc.description.upvformatpinicio 4035 es_ES
dc.description.upvformatpfin 4041 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 6 es_ES
dc.description.issue 7 es_ES
dc.relation.senia 297114 es_ES
dc.identifier.eissn 2041-6539
dc.contributor.funder Generalitat Valenciana es_ES
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