The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study

The potential tunability of the spectroscopic properties of the BODIPY parent dye by suitable functionalization makes it attractive for a number of applications. Unfortunately, its strong fluorescence against minor intersystem crossing to the triplet states prevents its application in photodynamic t...

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Detalles Bibliográficos
Autores: De Vetta, Martina, González, Leticia, Corral Pérez, Inés
Tipo de recurso: artículo
Fecha de publicación:2018
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/687606
Acceso en línea:http://hdl.handle.net/10486/687606
https://dx.doi.org/10.1002/cptc.201800169
Access Level:acceso abierto
Palabra clave:ADC(2) and CASPT2 calculations
BODIPY
Computational chemistry
Intersystem crossing
Photophysics
Potential energy surfaces
Química
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spelling The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 studyDe Vetta, MartinaGonzález, LeticiaCorral Pérez, InésADC(2) and CASPT2 calculationsBODIPYComputational chemistryIntersystem crossingPhotophysicsPotential energy surfacesQuímicaThe potential tunability of the spectroscopic properties of the BODIPY parent dye by suitable functionalization makes it attractive for a number of applications. Unfortunately, its strong fluorescence against minor intersystem crossing to the triplet states prevents its application in photodynamic therapy. With the perspective of designing BODIPY derivatives with enhanced intersystem crossing, the goal of this work is two-fold: (i) investigate the main deactivation channels of the parent BODIPY following irradiation, paying particular attention to the accessibility of the triplet state potential energy surfaces, as well as the non-radiative pathways involving the second brightest more stable singlet electronic state, S2, and (ii) evaluate the performance of the computationally efficient second order algebraic-diagrammatic construction scheme for the polarization propagator, (ADC(2)) against the complete active space second-order perturbation theory (CASPT2) method. Three singlet/triplet crossings were found, all of them with small spin-orbit couplings, being the S1/T2 crossing the most plausible for the observed intersystem crossing yield. Methodologically, it is found that the ADC(2) method qualitatively reproduces the landscape of the potential energy profiles for the photophysical processes investigated; however, it systematically underestimates the energies of the stationary points and crossings of the same and different multiplicity, with the largest discrepancies found at S1/S0 crossing points. Our CASPT2 results provide a comprehensive picture of the landscape of the excited state potential energy surfaces of the parent BODIPY that might serve as a basis for the rational design of photosensitizers with a particular photophysical profileThis 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 supportWiley‐VCH Verlag GmbH & Co. KGaA, WeinheimDepartamento de QuímicaFacultad de CienciasUAM. Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)20182018-10-08research articlehttp://purl.org/coar/resource_type/c_2df8fbb1SMURhttp://purl.org/coar/version/c_71e4c1898caa6e32info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/687606https://dx.doi.org/10.1002/cptc.201800169reponame: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:10486/6876062026-06-23T12:46:27Z
dc.title.none.fl_str_mv The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
title The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
spellingShingle The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
De Vetta, Martina
ADC(2) and CASPT2 calculations
BODIPY
Computational chemistry
Intersystem crossing
Photophysics
Potential energy surfaces
Química
title_short The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
title_full The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
title_fullStr The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
title_full_unstemmed The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
title_sort The role of electronic triplets and high-lying singlet states in the deactivation mechanism of the parent BODIPY: An ADC(2) and CASPT2 study
dc.creator.none.fl_str_mv De Vetta, Martina
González, Leticia
Corral Pérez, Inés
author De Vetta, Martina
author_facet De Vetta, Martina
González, Leticia
Corral Pérez, Inés
author_role author
author2 González, Leticia
Corral Pérez, Inés
author2_role author
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 ADC(2) and CASPT2 calculations
BODIPY
Computational chemistry
Intersystem crossing
Photophysics
Potential energy surfaces
Química
topic ADC(2) and CASPT2 calculations
BODIPY
Computational chemistry
Intersystem crossing
Photophysics
Potential energy surfaces
Química
description The potential tunability of the spectroscopic properties of the BODIPY parent dye by suitable functionalization makes it attractive for a number of applications. Unfortunately, its strong fluorescence against minor intersystem crossing to the triplet states prevents its application in photodynamic therapy. With the perspective of designing BODIPY derivatives with enhanced intersystem crossing, the goal of this work is two-fold: (i) investigate the main deactivation channels of the parent BODIPY following irradiation, paying particular attention to the accessibility of the triplet state potential energy surfaces, as well as the non-radiative pathways involving the second brightest more stable singlet electronic state, S2, and (ii) evaluate the performance of the computationally efficient second order algebraic-diagrammatic construction scheme for the polarization propagator, (ADC(2)) against the complete active space second-order perturbation theory (CASPT2) method. Three singlet/triplet crossings were found, all of them with small spin-orbit couplings, being the S1/T2 crossing the most plausible for the observed intersystem crossing yield. Methodologically, it is found that the ADC(2) method qualitatively reproduces the landscape of the potential energy profiles for the photophysical processes investigated; however, it systematically underestimates the energies of the stationary points and crossings of the same and different multiplicity, with the largest discrepancies found at S1/S0 crossing points. Our CASPT2 results provide a comprehensive picture of the landscape of the excited state potential energy surfaces of the parent BODIPY that might serve as a basis for the rational design of photosensitizers with a particular photophysical profile
publishDate 2018
dc.date.none.fl_str_mv 2018
2018-10-08
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/10486/687606
https://dx.doi.org/10.1002/cptc.201800169
url http://hdl.handle.net/10486/687606
https://dx.doi.org/10.1002/cptc.201800169
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 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
publisher.none.fl_str_mv Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
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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