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Photophysical properties of 5-substituted 2-thiopyrimidines

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Photophysical properties of 5-substituted 2-thiopyrimidines

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dc.contributor.author Vendrell Criado, Victoria es_ES
dc.contributor.author Sáez Cases, José Antonio es_ES
dc.contributor.author Lhiaubet, Virginie Lyria es_ES
dc.contributor.author Cuquerella Alabort, Maria Consuelo es_ES
dc.contributor.author Miranda Alonso, Miguel Ángel
dc.date.accessioned 2016-02-17T10:05:03Z
dc.date.available 2016-02-17T10:05:03Z
dc.date.issued 2013
dc.identifier.issn 1474-905X
dc.identifier.uri http://hdl.handle.net/10251/60952
dc.description.abstract The aim of the present work is to determine the influence of C5 substitution on the photophysical properties of 2-thiopyrimidines (2-TPyr). For this purpose, 2-thiouracil, 5-t-butyl-2-thiouracil and 2-thiothymine (TU, BTU and TT, respectively) have been selected as target thionucleobases for the experimental studies and, in parallel, for DFT theoretical calculations. The UV spectra displayed by TU, BTU and TT in EtOH were very similar to each other. They showed a maximum around 275 nm and a shoulder at ca. 290 nm. The three 2-TPyr exhibited a strong phosphorescence emission; from the recorded spectra, triplet excited state energies of ca. 307, 304 and 294 kJ mol(-1) were determined for TU, BTU and TT, respectively. Laser excitation at 308 nm gave rise to a broad transient absorption band from 500 nm to 700 nm, which was in principle assigned to triplet-triplet absorption. This assignment was confirmed by energy transfer experiments using biphenyl (E-T = 274 kJ mol(-1)) as an acceptor. The triplet lifetimes were 70 ns, 1.1 mu s and 2.3 mu s, for TU, BTU and TT, respectively. The obtained photophysical data, both in phosphorescence and transient absorption measurements, point to significantly different properties of the TT triplet excited state in spite of the structural similarities. Theoretical calculations at the B3LYP/aug-cc-pVDZ/PCM level agree well with the experimental range of excited state energies and support the pi pi(star) nature of the lowest triplet states. es_ES
dc.description.sponsorship Financial support by the Spanish Government (CTQ2009-13699, CTQ2012-32621, RyC-2007-00476 to V. L.-V., and contracts JAE-Predoc 2011-00740 and JAE-Doc 2010-06204 to V. V.-C. and J. A. S. respectively) and the computing facilities provided by the Theoretical Organic Chemistry group at the Universitat de Valencia (http://utopia.uv.es) are acknowledged. en_EN
dc.language Inglés es_ES
dc.publisher Royal Society of Chemistry es_ES
dc.relation Spanish Government CTQ2009-13699 CTQ2012-32621 RyC-2007-00476 JAE-Predoc 2011-00740 JAE-Doc 2010-06204 es_ES
dc.relation.ispartof Photochemical & Photobiological Sciences Photochemical and Photobiological Sciences es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject DENSITY-FUNCTIONAL THEORY es_ES
dc.subject POLARIZABLE CONTINUUM MODEL es_ES
dc.subject EXCITATION-ENERGIES es_ES
dc.subject GEOMETRIC DERIVATIVES es_ES
dc.subject ANTITHYROID DRUGS es_ES
dc.subject APPROXIMATION es_ES
dc.subject MOLECULES es_ES
dc.subject PROTEIN es_ES
dc.subject STATES es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.subject.classification QUIMICA ANALITICA es_ES
dc.title Photophysical properties of 5-substituted 2-thiopyrimidines es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1039/c3pp50058f
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 Vendrell Criado, V.; Sáez Cases, JA.; Lhiaubet, VL.; Cuquerella Alabort, MC.; Miranda Alonso, MÁ. (2013). Photophysical properties of 5-substituted 2-thiopyrimidines. Photochemical & Photobiological Sciences Photochemical and Photobiological Sciences. 12(8):1460-1465. doi:10.1039/c3pp50058f es_ES
dc.description.accrualMethod Senia es_ES
dc.relation.publisherversion http://dx.doi.org/10.1039/c3pp50058f es_ES
dc.description.upvformatpinicio 1460 es_ES
dc.description.upvformatpfin 1465 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 12 es_ES
dc.description.issue 8 es_ES
dc.relation.senia 256842 es_ES
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