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

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 in...

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Authors: De Vetta, Martina, Corral Pérez, Inés
Format: article
Publication Date:2019
Country:España
Institution:Universidad Autónoma de Madrid
Repository:Biblos-e Archivo. Repositorio Institucional de la UAM
Language:English
OAI Identifier:oai:repositorio.uam.es:10486/687604
Online Access:http://hdl.handle.net/10486/687604
https://dx.doi.org/10.1016/j.comptc.2019.01.014
Access Level:Open access
Keyword:Absorption spectrum
ADC(2)
Emission
Meso-substituted BODIPYs
CASPT2
Química
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spelling Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyesDe Vetta, MartinaCorral Pérez, InésAbsorption spectrumADC(2)EmissionMeso-substituted BODIPYsCASPT2QuímicaThe 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.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 supportElsevierDepartamento de QuímicaFacultad de CienciasUAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)20192019-02-15research articlehttp://purl.org/coar/resource_type/c_2df8fbb1SMURhttp://purl.org/coar/version/c_71e4c1898caa6e32info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/687604https://dx.doi.org/10.1016/j.comptc.2019.01.014reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6876042026-06-23T12:46:27Z
dc.title.none.fl_str_mv Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
title Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
spellingShingle Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
De Vetta, Martina
Absorption spectrum
ADC(2)
Emission
Meso-substituted BODIPYs
CASPT2
Química
title_short Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
title_full Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
title_fullStr Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
title_full_unstemmed Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
title_sort Insight into the optical properties of meso-pentafluorophenyl(PFP)-BODIPY: An attractive platform for functionalization of BODIPY dyes
dc.creator.none.fl_str_mv De Vetta, Martina
Corral Pérez, Inés
author De Vetta, Martina
author_facet De Vetta, Martina
Corral Pérez, Inés
author_role author
author2 Corral Pérez, Inés
author2_role author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
UAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)
dc.subject.none.fl_str_mv Absorption spectrum
ADC(2)
Emission
Meso-substituted BODIPYs
CASPT2
Química
topic Absorption spectrum
ADC(2)
Emission
Meso-substituted BODIPYs
CASPT2
Química
description 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.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019-02-15
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
SMUR
http://purl.org/coar/version/c_71e4c1898caa6e32
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/687604
https://dx.doi.org/10.1016/j.comptc.2019.01.014
url http://hdl.handle.net/10486/687604
https://dx.doi.org/10.1016/j.comptc.2019.01.014
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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