Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species

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Photoexcitation of [Ru(tpy)(bpy)(μ-CN)Ru(py) 4 Cl] 2+ ([RuRu] 2+ ) at 387 nm results in the population of two 3 MLCT excited states of different symmetry that coexist on the nanosecond scale. Common to both states is an excited electron in a tpy-based orbital. Their configuration differs in the posi...

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Autores principales: Oviedo, P.S., Pieslinger, G.E., Baraldo, L.M., Cadranel, A., Guldi, D.M.
Formato: JOUR
Materias:
Charge transfer
Ground state
Infrared devices
Intermetallics
Photoexcitation
Wave functions
Electronic interactions
Excited electrons
Interconversions
Intervalence charge transfer
Metal centers
MLCT excited state
Photo-induced
Single molecular species
Excited states
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_19327447_v123_n6_p3285_Oviedo
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_19327447_v123_n6_p3285_Oviedo2023-10-03T16:36:09Z Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species Oviedo, P.S. Pieslinger, G.E. Baraldo, L.M. Cadranel, A. Guldi, D.M. Charge transfer Ground state Infrared devices Intermetallics Photoexcitation Wave functions Electronic interactions Excited electrons Interconversions Intervalence charge transfer Metal centers MLCT excited state Photo-induced Single molecular species Excited states Photoexcitation of [Ru(tpy)(bpy)(μ-CN)Ru(py) 4 Cl] 2+ ([RuRu] 2+ ) at 387 nm results in the population of two 3 MLCT excited states of different symmetry that coexist on the nanosecond scale. Common to both states is an excited electron in a tpy-based orbital. Their configuration differs in the position of the hole. In one excited state, 3 MLCTz, the hole sits in an orbital parallel to the intermetallic axis allowing for a strong metal-metal electronic interaction. As a result, 3 MLCTz is highly delocalized over both metal centers and shows an intense photoinduced intervalence charge transfer (PIIVCT) NIR signature. In the other excited state, 3 MLCTxy, the hole is localized in an orbital perpendicular to the intermetallic axis and hence, significant intermetallic coupling is absent. This state shows no PIIVCT in the NIR and its spectrum is very similar to the one observed for the monometallic [Ru(tpy)(bpy)(CN)] + reference. Both 3 MLCT excited states have nanosecond lifetimes. The intervening energy barrier for a hole reconfiguration between the two different 3 MLCT excited states offers the opportunity to exploit wave functions of different symmetry before either the interconversion between them or the decay to the ground state is operative. © 2019 American Chemical Society. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_19327447_v123_n6_p3285_Oviedo
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Charge transfer
Ground state
Infrared devices
Intermetallics
Photoexcitation
Wave functions
Electronic interactions
Excited electrons
Interconversions
Intervalence charge transfer
Metal centers
MLCT excited state
Photo-induced
Single molecular species
Excited states
spellingShingle Charge transfer
Ground state
Infrared devices
Intermetallics
Photoexcitation
Wave functions
Electronic interactions
Excited electrons
Interconversions
Intervalence charge transfer
Metal centers
MLCT excited state
Photo-induced
Single molecular species
Excited states
Oviedo, P.S.
Pieslinger, G.E.
Baraldo, L.M.
Cadranel, A.
Guldi, D.M.
Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
topic_facet Charge transfer
Ground state
Infrared devices
Intermetallics
Photoexcitation
Wave functions
Electronic interactions
Excited electrons
Interconversions
Intervalence charge transfer
Metal centers
MLCT excited state
Photo-induced
Single molecular species
Excited states
description Photoexcitation of [Ru(tpy)(bpy)(μ-CN)Ru(py) 4 Cl] 2+ ([RuRu] 2+ ) at 387 nm results in the population of two 3 MLCT excited states of different symmetry that coexist on the nanosecond scale. Common to both states is an excited electron in a tpy-based orbital. Their configuration differs in the position of the hole. In one excited state, 3 MLCTz, the hole sits in an orbital parallel to the intermetallic axis allowing for a strong metal-metal electronic interaction. As a result, 3 MLCTz is highly delocalized over both metal centers and shows an intense photoinduced intervalence charge transfer (PIIVCT) NIR signature. In the other excited state, 3 MLCTxy, the hole is localized in an orbital perpendicular to the intermetallic axis and hence, significant intermetallic coupling is absent. This state shows no PIIVCT in the NIR and its spectrum is very similar to the one observed for the monometallic [Ru(tpy)(bpy)(CN)] + reference. Both 3 MLCT excited states have nanosecond lifetimes. The intervening energy barrier for a hole reconfiguration between the two different 3 MLCT excited states offers the opportunity to exploit wave functions of different symmetry before either the interconversion between them or the decay to the ground state is operative. © 2019 American Chemical Society.
format JOUR
author Oviedo, P.S.
Pieslinger, G.E.
Baraldo, L.M.
Cadranel, A.
Guldi, D.M.
author_facet Oviedo, P.S.
Pieslinger, G.E.
Baraldo, L.M.
Cadranel, A.
Guldi, D.M.
author_sort Oviedo, P.S.
title Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
title_short Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
title_full Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
title_fullStr Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
title_full_unstemmed Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species
title_sort coexistence of mlct excited states of different symmetry upon photoexcitation of a single molecular species
url http://hdl.handle.net/20.500.12110/paper_19327447_v123_n6_p3285_Oviedo
work_keys_str_mv AT oviedops coexistenceofmlctexcitedstatesofdifferentsymmetryuponphotoexcitationofasinglemolecularspecies
AT pieslingerge coexistenceofmlctexcitedstatesofdifferentsymmetryuponphotoexcitationofasinglemolecularspecies
AT baraldolm coexistenceofmlctexcitedstatesofdifferentsymmetryuponphotoexcitationofasinglemolecularspecies
AT cadranela coexistenceofmlctexcitedstatesofdifferentsymmetryuponphotoexcitationofasinglemolecularspecies
AT guldidm coexistenceofmlctexcitedstatesofdifferentsymmetryuponphotoexcitationofasinglemolecularspecies
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