Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes

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dc.contributor.author De Vetta, Martina
dc.contributor.author Corral, Inés
dc.contributor.other UAM. Departamento de Química es_ES
dc.contributor.other Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem) es_ES
dc.date.accessioned 2019-05-23T13:26:21Z
dc.date.available 2019-05-23T13:26:21Z
dc.date.issued 2019-02-15
dc.identifier.citation Computational and Theoretical Chemistry 1150 (2018): 110-120 en_US
dc.identifier.issn 2210-271X es_ES
dc.identifier.uri http://hdl.handle.net/10486/687604
dc.description.abstract The pentafluorophenyl (PFP) moiety is an important and versatile substituent in the chemistry of BODIPYs, porphyrins and corroles. The widespread use of PFP meso-substituted compounds, as intermediates in the synthesis of more complex pyrrole derivatives, is the motivation behind this work, which investigates the optical properties of the meso-PFP-BODIPY from a theoretical point of view. From the panoply of computational tools available for this purpose, we have considered the MS-CASPT2//CASSCF multiconfigurational protocol, and other monoreference methods, including time dependent density functional theory, TD-DFT, the second order approximate couple cluster, CC2, and the algebraic diagrammatic construction scheme of the polarization propagator in its second order, ADC(2). We have identified ADC(2) as the most suited method for the characterization of the absorption properties of BODIPYs. Besides its computational efficiency and the small dependence shown towards the basis set flexibility, the results obtained with this method are independent from the preexisting knowledge of the system and its properties to be calculated by the user. In general, all the methods evaluated show a good performance when compared with experimental results, especially if implicit solvent effects are taken into account, delivering errors which amount to 0.05 eV. Finally, we discuss the effect of the electron-withdrawing PFP substituent at the meso-position on the absorption and emission energies of the boron-dipyrromethene core. The comparison of the PFP-substituted and core BODIPY spectroscopic properties reveals that this substituent red-shifts both the absorption and the emission of the parent dye. On the one hand, the incorporation of this substituent was found to reduce the HOMO-LUMO gap, and on the other it induces a strong destabilization of the electronic ground state along the global coordinate leading the system from the Franck-Condon region to the position of the first excited state, S1, minimum, suggesting a lower S1/S0 internal conversion funnel compared to the parent BODIPY compound. en_US
dc.description.sponsorship This work has been supported by the Project CTQ2015-63997- C2 of the Ministerio de Economía y Competitividad of Spain. I.C. gratefully acknowledges the “Ramón y Cajal” program of the Ministerio de Economía y Competitividad of Spain. M.D.V. thanks the Marie Curie Actions, within the Innovative Training Network-European Join Doctorate in Theoretical Chemistry and Computational Modelling TCCM-ITN-EJD-642294, for financial support en_US
dc.format.extent 41 pag. es_ES
dc.format.mimetype application/pdf en
dc.language.iso eng en
dc.publisher Elsevier en_US
dc.relation.ispartof Computational and Theoretical Chemistry en_US
dc.rights © 2019 es_ES
dc.subject.other Absorption spectrum en_US
dc.subject.other ADC(2) en_US
dc.subject.other CASPT2 es_ES
dc.subject.other Emission en_US
dc.subject.other Meso-substituted BODIPYs en_US
dc.title Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes en_US
dc.type article en
dc.subject.eciencia Química es_ES
dc.relation.publisherversion https://doi.org/10.1016/j.comptc.2019.01.014 es_ES
dc.identifier.doi 10.1016/j.comptc.2019.01.014 es_ES
dc.identifier.publicationfirstpage 110 es_ES
dc.identifier.publicationlastpage 120 es_ES
dc.relation.projectID Gobierno de España. CTQ2015-63997- C2 es_ES
dc.type.version info:eu-repo/semantics/submittedVersion en
dc.rights.accessRights openAccess en


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