Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study

Autores
Martínez Saavedra, Héctor Hernando; Ragone, Fabricio; Franca, Carlos Alberto; Ruiz, Gustavo Teodosio; David Gara, Pedro Maximiliano; Wolcan, Ezequiel
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The photophysical properties of the complex Bu₄N[(4,4′-bpy)Re(CO)₃(bpy-5,5′-diCOO)] were studied in protic and aprotic media with the aid of steady-state and time-resolved techniques and TD-DFT calculations. The absorption spectrum as well as the steady state and time resolved luminescence of the Re(I) complex display a marked solvent effect. The highest and lowest energy absorption bands experience a bathochromic shift as the polarity of the solvent decreases. In addition, the lowest energy band broadens. Two luminescence bands were observed around 430 and 600 nm in protic organic solvents like alcohols. The high energy emission is observed solely in aqueous solutions, while in aprotic solvents only the low energy luminescence is detected. TD-DFT calculations allowed us to identify the main electronic transitions in the low energy region as ¹MLLCT Re(CO)₃ → 4,4′-bpy and ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO. The simulated absorption spectra of the Re(I) complex in H2O, protic (EtOH, MeOH) and aprotic (CHCl₃, CH₂Cl₂, CH₃CN) organic solvents follow the experimental absorption spectra with reasonable accuracy both in position and relative intensities. The magnitude of the calculated dipole moment (μ) increases with the dielectric constant of the solvent (εr). Besides, the energy of ¹MLLCT Re(CO)₃ → 4,4′-bpy also increases with εr. However, the energy of the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is rather insensitive to εr. This disparity is attributed to the fact that the ¹MLLCT Re(CO)₃ → 4,4′-bpy transition is nearly parallel to the orientation of μ while the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is almost perpendicular to it. Unrestricted TD-DFT calculations were successfully applied to the triplet species. It is observed that in the triplet state the Re–N distances are shortened while Re–C distances are elongated relative to the ground state. The calculated emission energy by TD-DFT and/or Δ(SCF) methods was compared to the experimental emission maximum in chloroform. All the experimental results as well as the theoretical calculations indicate that solvent effects on the steady state and time resolved luminescence of the Re(I) complex can be accounted by the coexistence of ³MLLCT Re(CO)₃ → 4,4′-bpy, ³MLLCT Re(CO)₃ → bpy-5,5′-diCOO and ¹IL excited states.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Centro de Química Inorgánica
Centro de Investigaciones Ópticas
Laboratorio de Ablación Láser, Fotónica e Imágenes 3D
Materia
Física
Química
Re(I) tricarbonyl complex
Solvent effects
TD-DFT
Photophysics
Triplet energy calculation
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/151501

id SEDICI_5014c608a866de87e3f7f31ad44c14a1
oai_identifier_str oai:sedici.unlp.edu.ar:10915/151501
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational studyMartínez Saavedra, Héctor HernandoRagone, FabricioFranca, Carlos AlbertoRuiz, Gustavo TeodosioDavid Gara, Pedro MaximilianoWolcan, EzequielFísicaQuímicaRe(I) tricarbonyl complexSolvent effectsTD-DFTPhotophysicsTriplet energy calculationThe photophysical properties of the complex Bu₄N[(4,4′-bpy)Re(CO)₃(bpy-5,5′-diCOO)] were studied in protic and aprotic media with the aid of steady-state and time-resolved techniques and TD-DFT calculations. The absorption spectrum as well as the steady state and time resolved luminescence of the Re(I) complex display a marked solvent effect. The highest and lowest energy absorption bands experience a bathochromic shift as the polarity of the solvent decreases. In addition, the lowest energy band broadens. Two luminescence bands were observed around 430 and 600 nm in protic organic solvents like alcohols. The high energy emission is observed solely in aqueous solutions, while in aprotic solvents only the low energy luminescence is detected. TD-DFT calculations allowed us to identify the main electronic transitions in the low energy region as ¹MLLCT Re(CO)₃ → 4,4′-bpy and ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO. The simulated absorption spectra of the Re(I) complex in H2O, protic (EtOH, MeOH) and aprotic (CHCl₃, CH₂Cl₂, CH₃CN) organic solvents follow the experimental absorption spectra with reasonable accuracy both in position and relative intensities. The magnitude of the calculated dipole moment (μ) increases with the dielectric constant of the solvent (εr). Besides, the energy of ¹MLLCT Re(CO)₃ → 4,4′-bpy also increases with εr. However, the energy of the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is rather insensitive to εr. This disparity is attributed to the fact that the ¹MLLCT Re(CO)₃ → 4,4′-bpy transition is nearly parallel to the orientation of μ while the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is almost perpendicular to it. Unrestricted TD-DFT calculations were successfully applied to the triplet species. It is observed that in the triplet state the Re–N distances are shortened while Re–C distances are elongated relative to the ground state. The calculated emission energy by TD-DFT and/or Δ(SCF) methods was compared to the experimental emission maximum in chloroform. All the experimental results as well as the theoretical calculations indicate that solvent effects on the steady state and time resolved luminescence of the Re(I) complex can be accounted by the coexistence of ³MLLCT Re(CO)₃ → 4,4′-bpy, ³MLLCT Re(CO)₃ → bpy-5,5′-diCOO and ¹IL excited states.Instituto de Investigaciones Fisicoquímicas Teóricas y AplicadasCentro de Química InorgánicaCentro de Investigaciones ÓpticasLaboratorio de Ablación Láser, Fotónica e Imágenes 3D2016-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf26-35http://sedici.unlp.edu.ar/handle/10915/151501enginfo:eu-repo/semantics/altIdentifier/issn/0022-328Xinfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2016.05.012info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/4.0/Creative Commons Attribution 4.0 International (CC BY 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:39:02Zoai:sedici.unlp.edu.ar:10915/151501Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:39:02.63SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
title Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
spellingShingle Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
Martínez Saavedra, Héctor Hernando
Física
Química
Re(I) tricarbonyl complex
Solvent effects
TD-DFT
Photophysics
Triplet energy calculation
title_short Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
title_full Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
title_fullStr Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
title_full_unstemmed Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
title_sort Solvent effects on the photophysical properties of Bu₄N[(4,40-bpy) Re(CO)₃(bpy-5,50-diCOO)] complex : A combined experimental and computational study
dc.creator.none.fl_str_mv Martínez Saavedra, Héctor Hernando
Ragone, Fabricio
Franca, Carlos Alberto
Ruiz, Gustavo Teodosio
David Gara, Pedro Maximiliano
Wolcan, Ezequiel
author Martínez Saavedra, Héctor Hernando
author_facet Martínez Saavedra, Héctor Hernando
Ragone, Fabricio
Franca, Carlos Alberto
Ruiz, Gustavo Teodosio
David Gara, Pedro Maximiliano
Wolcan, Ezequiel
author_role author
author2 Ragone, Fabricio
Franca, Carlos Alberto
Ruiz, Gustavo Teodosio
David Gara, Pedro Maximiliano
Wolcan, Ezequiel
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Física
Química
Re(I) tricarbonyl complex
Solvent effects
TD-DFT
Photophysics
Triplet energy calculation
topic Física
Química
Re(I) tricarbonyl complex
Solvent effects
TD-DFT
Photophysics
Triplet energy calculation
dc.description.none.fl_txt_mv The photophysical properties of the complex Bu₄N[(4,4′-bpy)Re(CO)₃(bpy-5,5′-diCOO)] were studied in protic and aprotic media with the aid of steady-state and time-resolved techniques and TD-DFT calculations. The absorption spectrum as well as the steady state and time resolved luminescence of the Re(I) complex display a marked solvent effect. The highest and lowest energy absorption bands experience a bathochromic shift as the polarity of the solvent decreases. In addition, the lowest energy band broadens. Two luminescence bands were observed around 430 and 600 nm in protic organic solvents like alcohols. The high energy emission is observed solely in aqueous solutions, while in aprotic solvents only the low energy luminescence is detected. TD-DFT calculations allowed us to identify the main electronic transitions in the low energy region as ¹MLLCT Re(CO)₃ → 4,4′-bpy and ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO. The simulated absorption spectra of the Re(I) complex in H2O, protic (EtOH, MeOH) and aprotic (CHCl₃, CH₂Cl₂, CH₃CN) organic solvents follow the experimental absorption spectra with reasonable accuracy both in position and relative intensities. The magnitude of the calculated dipole moment (μ) increases with the dielectric constant of the solvent (εr). Besides, the energy of ¹MLLCT Re(CO)₃ → 4,4′-bpy also increases with εr. However, the energy of the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is rather insensitive to εr. This disparity is attributed to the fact that the ¹MLLCT Re(CO)₃ → 4,4′-bpy transition is nearly parallel to the orientation of μ while the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is almost perpendicular to it. Unrestricted TD-DFT calculations were successfully applied to the triplet species. It is observed that in the triplet state the Re–N distances are shortened while Re–C distances are elongated relative to the ground state. The calculated emission energy by TD-DFT and/or Δ(SCF) methods was compared to the experimental emission maximum in chloroform. All the experimental results as well as the theoretical calculations indicate that solvent effects on the steady state and time resolved luminescence of the Re(I) complex can be accounted by the coexistence of ³MLLCT Re(CO)₃ → 4,4′-bpy, ³MLLCT Re(CO)₃ → bpy-5,5′-diCOO and ¹IL excited states.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Centro de Química Inorgánica
Centro de Investigaciones Ópticas
Laboratorio de Ablación Láser, Fotónica e Imágenes 3D
description The photophysical properties of the complex Bu₄N[(4,4′-bpy)Re(CO)₃(bpy-5,5′-diCOO)] were studied in protic and aprotic media with the aid of steady-state and time-resolved techniques and TD-DFT calculations. The absorption spectrum as well as the steady state and time resolved luminescence of the Re(I) complex display a marked solvent effect. The highest and lowest energy absorption bands experience a bathochromic shift as the polarity of the solvent decreases. In addition, the lowest energy band broadens. Two luminescence bands were observed around 430 and 600 nm in protic organic solvents like alcohols. The high energy emission is observed solely in aqueous solutions, while in aprotic solvents only the low energy luminescence is detected. TD-DFT calculations allowed us to identify the main electronic transitions in the low energy region as ¹MLLCT Re(CO)₃ → 4,4′-bpy and ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO. The simulated absorption spectra of the Re(I) complex in H2O, protic (EtOH, MeOH) and aprotic (CHCl₃, CH₂Cl₂, CH₃CN) organic solvents follow the experimental absorption spectra with reasonable accuracy both in position and relative intensities. The magnitude of the calculated dipole moment (μ) increases with the dielectric constant of the solvent (εr). Besides, the energy of ¹MLLCT Re(CO)₃ → 4,4′-bpy also increases with εr. However, the energy of the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is rather insensitive to εr. This disparity is attributed to the fact that the ¹MLLCT Re(CO)₃ → 4,4′-bpy transition is nearly parallel to the orientation of μ while the ¹MLLCT Re(CO)₃ → bpy-5,5′-diCOO transition is almost perpendicular to it. Unrestricted TD-DFT calculations were successfully applied to the triplet species. It is observed that in the triplet state the Re–N distances are shortened while Re–C distances are elongated relative to the ground state. The calculated emission energy by TD-DFT and/or Δ(SCF) methods was compared to the experimental emission maximum in chloroform. All the experimental results as well as the theoretical calculations indicate that solvent effects on the steady state and time resolved luminescence of the Re(I) complex can be accounted by the coexistence of ³MLLCT Re(CO)₃ → 4,4′-bpy, ³MLLCT Re(CO)₃ → bpy-5,5′-diCOO and ¹IL excited states.
publishDate 2016
dc.date.none.fl_str_mv 2016-08
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/151501
url http://sedici.unlp.edu.ar/handle/10915/151501
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/0022-328X
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2016.05.012
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/4.0/
Creative Commons Attribution 4.0 International (CC BY 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/4.0/
Creative Commons Attribution 4.0 International (CC BY 4.0)
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