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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/151501
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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 Articulo http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
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 |
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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) |
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openAccess |
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http://creativecommons.org/licenses/by/4.0/ Creative Commons Attribution 4.0 International (CC BY 4.0) |
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application/pdf 26-35 |
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