Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity

The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniq...

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Autores principales:	Iván Maisuls, Ezequiel Wolcan, Pedro M. David-Gara, Franco M. Cabrerizo, Guillermo J. Ferraudi, Gustavo T. Ruiz
Formato:	article
Lenguaje:	EN
Publicado:	Elsevier 2021
Materias:	Rhenium tricarbonyl complexes Singlet oxygen generation Photophysics Photochemistry Norharmane – TD-DFT Pulse radiolysis Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/61346c5b739c4b448267aa06d520947f
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spelling	oai:doaj.org-article:61346c5b739c4b448267aa06d520947f2021-11-04T04:40:21ZPhotophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity2666-469010.1016/j.jpap.2021.100078https://doaj.org/article/61346c5b739c4b448267aa06d520947f2021-12-01T00:00:00Zhttp://www.sciencedirect.com/science/article/pii/S2666469021000634https://doaj.org/toc/2666-4690The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. These results allowed us to identify and study the reactivity of the β-carboline (nHo) Rhenium(I) complex main excited states. The absorption spectrum as well as the steady-state and time-resolved luminescence of the complex exhibits a marked dependence with the solvent properties. These experimentally observed results were corroborated by quantum chemical calculations, TD-DFT. The most important electronic transitions present in the spectrum in all solvents are MLLCTRe(CO)3→nHo1, nHo2 along with a mixture of ILnHo and LLCTCl→nHo transitions. The relationship between the dipole moment and the polarity of the solvent was rationalized in terms of the electron density inside and outside the complex. While the luminescence of the complex is mainly attributed to the emitting 1ILnHo state, in LFP experiments a MLCT excited state was also detected. The species generated in either reductive or oxidative conditions in LFP experiments were compared with those obtained in PR. Also, the quenching rate constant (kq) of the excited state with MV+2 was calculated. The excited state of the complex can efficiently generate singlet oxygen in acetonitrile yielding a ΦΔ = 0.25 ± 0.02. Optoacoustic measurements showed that, after photonic excitation, almost all the absorbed energy by the complex is released to the medium as prompt heat. The investigated photophysical and photochemical properties of ClRe(CO)3(nHo)2 are of significant importance in relation to the use of this β-carboline Rhenium(I) complex in several biomedical fields, such as photodynamic therapy and photoactivated chemotherapy as well as new alternative therapies such as regional hyperthermia.Iván MaisulsEzequiel WolcanPedro M. David-GaraFranco M. CabrerizoGuillermo J. FerraudiGustavo T. RuizElsevierarticleRhenium tricarbonyl complexesSinglet oxygen generationPhotophysicsPhotochemistryNorharmane – TD-DFTPulse radiolysisChemistryQD1-999ENJournal of Photochemistry and Photobiology, Vol 8, Iss , Pp 100078- (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Rhenium tricarbonyl complexes Singlet oxygen generation Photophysics Photochemistry Norharmane – TD-DFT Pulse radiolysis Chemistry QD1-999
spellingShingle	Rhenium tricarbonyl complexes Singlet oxygen generation Photophysics Photochemistry Norharmane – TD-DFT Pulse radiolysis Chemistry QD1-999 Iván Maisuls Ezequiel Wolcan Pedro M. David-Gara Franco M. Cabrerizo Guillermo J. Ferraudi Gustavo T. Ruiz Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
description	The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. These results allowed us to identify and study the reactivity of the β-carboline (nHo) Rhenium(I) complex main excited states. The absorption spectrum as well as the steady-state and time-resolved luminescence of the complex exhibits a marked dependence with the solvent properties. These experimentally observed results were corroborated by quantum chemical calculations, TD-DFT. The most important electronic transitions present in the spectrum in all solvents are MLLCTRe(CO)3→nHo1, nHo2 along with a mixture of ILnHo and LLCTCl→nHo transitions. The relationship between the dipole moment and the polarity of the solvent was rationalized in terms of the electron density inside and outside the complex. While the luminescence of the complex is mainly attributed to the emitting 1ILnHo state, in LFP experiments a MLCT excited state was also detected. The species generated in either reductive or oxidative conditions in LFP experiments were compared with those obtained in PR. Also, the quenching rate constant (kq) of the excited state with MV+2 was calculated. The excited state of the complex can efficiently generate singlet oxygen in acetonitrile yielding a ΦΔ = 0.25 ± 0.02. Optoacoustic measurements showed that, after photonic excitation, almost all the absorbed energy by the complex is released to the medium as prompt heat. The investigated photophysical and photochemical properties of ClRe(CO)3(nHo)2 are of significant importance in relation to the use of this β-carboline Rhenium(I) complex in several biomedical fields, such as photodynamic therapy and photoactivated chemotherapy as well as new alternative therapies such as regional hyperthermia.
format	article
author	Iván Maisuls Ezequiel Wolcan Pedro M. David-Gara Franco M. Cabrerizo Guillermo J. Ferraudi Gustavo T. Ruiz
author_facet	Iván Maisuls Ezequiel Wolcan Pedro M. David-Gara Franco M. Cabrerizo Guillermo J. Ferraudi Gustavo T. Ruiz
author_sort	Iván Maisuls
title	Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_short	Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_full	Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_fullStr	Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_full_unstemmed	Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_sort	photophysical properties of a β-carboline rhenium (i) complex. solvent effects on excited states and their redox reactivity
publisher	Elsevier
publishDate	2021
url	https://doaj.org/article/61346c5b739c4b448267aa06d520947f
work_keys_str_mv	AT ivanmaisuls photophysicalpropertiesofabcarbolinerheniumicomplexsolventeffectsonexcitedstatesandtheirredoxreactivity AT ezequielwolcan photophysicalpropertiesofabcarbolinerheniumicomplexsolventeffectsonexcitedstatesandtheirredoxreactivity AT pedromdavidgara photophysicalpropertiesofabcarbolinerheniumicomplexsolventeffectsonexcitedstatesandtheirredoxreactivity AT francomcabrerizo photophysicalpropertiesofabcarbolinerheniumicomplexsolventeffectsonexcitedstatesandtheirredoxreactivity AT guillermojferraudi photophysicalpropertiesofabcarbolinerheniumicomplexsolventeffectsonexcitedstatesandtheirredoxreactivity AT gustavotruiz photophysicalpropertiesofabcarbolinerheniumicomplexsolventeffectsonexcitedstatesandtheirredoxreactivity
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Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity

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