A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization

A new water soluble Re(I) complex with a zwitterionic structure, Bu₄N[(bpy)Re(CO)₃(dcbpy)] (where Bu = butyl; bpy = 4,4′-bipyridine; dcbpy = 2,2′-bipyridine-5,5′-dicarboxylate), was successfully synthesized and characterized by elemental analysis, ¹H NMR, FTIR and ESI. Protonation studies in aqueous...

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Autores principales: Martínez Saavedra, Héctor Hernando, Franca, Carlos Alberto, Petroselli, Gabriela, Erra-Balsells, Rosa, Ruiz, Gustavo Teodosio, Wolcan, Ezequiel
Formato: Articulo
Lenguaje:Inglés
Publicado: 2013
Materias:
Ciencias Exactas
Química
Re(I) complex
Zwitterionic
MLLCT
TD-DFT
Acidebase equilibriums
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/151450
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-151450
record_format dspace
spelling I19-R120-10915-1514502023-04-13T20:40:30Z http://sedici.unlp.edu.ar/handle/10915/151450 issn:0022-328X A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization Martínez Saavedra, Héctor Hernando Franca, Carlos Alberto Petroselli, Gabriela Erra-Balsells, Rosa Ruiz, Gustavo Teodosio Wolcan, Ezequiel 2013-11 2023-04-13T18:31:23Z en Ciencias Exactas Química Re(I) complex Zwitterionic MLLCT TD-DFT Acidebase equilibriums A new water soluble Re(I) complex with a zwitterionic structure, Bu₄N[(bpy)Re(CO)₃(dcbpy)] (where Bu = butyl; bpy = 4,4′-bipyridine; dcbpy = 2,2′-bipyridine-5,5′-dicarboxylate), was successfully synthesized and characterized by elemental analysis, ¹H NMR, FTIR and ESI. Protonation studies in aqueous solutions of the Re(I) complex showed three acid–base equilibriums with pKₐ₁ = 5.0, pKₐ₂ = 3.0 and pKₐ₃ = 2.0. pKₐ₁ was assigned to the protonation equilibrium at bpy while pKₐ₂ and pKₐ₃ could be ascribed to protonation/deprotonation of the two carboxylates groups in the dcbpy ligand. With the aid of TD-DFT calculations the nature of the electronic transitions responsible for the pH-dependent UV–vis spectroscopy of the Re(I) complex was identified. At pH = 7 the lower energy band of the complex has MLLCTRe(CO)3→dcbpy character while at pH < 2 it switches to MLLCTRe(CO)3→bpy. This change in the nature of the lower energy band is responsible for the overall spectral changes in the 350–500 nm range after protonation of the Re(I) complex. Centro de Química Inorgánica Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Articulo Articulo http://creativecommons.org/licenses/by/4.0/ Creative Commons Attribution 4.0 International (CC BY 4.0) application/pdf 470-478
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Ciencias Exactas
Química
Re(I) complex
Zwitterionic
MLLCT
TD-DFT
Acidebase equilibriums
spellingShingle Ciencias Exactas
Química
Re(I) complex
Zwitterionic
MLLCT
TD-DFT
Acidebase equilibriums
Martínez Saavedra, Héctor Hernando
Franca, Carlos Alberto
Petroselli, Gabriela
Erra-Balsells, Rosa
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
topic_facet Ciencias Exactas
Química
Re(I) complex
Zwitterionic
MLLCT
TD-DFT
Acidebase equilibriums
description A new water soluble Re(I) complex with a zwitterionic structure, Bu₄N[(bpy)Re(CO)₃(dcbpy)] (where Bu = butyl; bpy = 4,4′-bipyridine; dcbpy = 2,2′-bipyridine-5,5′-dicarboxylate), was successfully synthesized and characterized by elemental analysis, ¹H NMR, FTIR and ESI. Protonation studies in aqueous solutions of the Re(I) complex showed three acid–base equilibriums with pKₐ₁ = 5.0, pKₐ₂ = 3.0 and pKₐ₃ = 2.0. pKₐ₁ was assigned to the protonation equilibrium at bpy while pKₐ₂ and pKₐ₃ could be ascribed to protonation/deprotonation of the two carboxylates groups in the dcbpy ligand. With the aid of TD-DFT calculations the nature of the electronic transitions responsible for the pH-dependent UV–vis spectroscopy of the Re(I) complex was identified. At pH = 7 the lower energy band of the complex has MLLCTRe(CO)3→dcbpy character while at pH < 2 it switches to MLLCTRe(CO)3→bpy. This change in the nature of the lower energy band is responsible for the overall spectral changes in the 350–500 nm range after protonation of the Re(I) complex.
format Articulo
Articulo
author Martínez Saavedra, Héctor Hernando
Franca, Carlos Alberto
Petroselli, Gabriela
Erra-Balsells, Rosa
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author_facet Martínez Saavedra, Héctor Hernando
Franca, Carlos Alberto
Petroselli, Gabriela
Erra-Balsells, Rosa
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author_sort Martínez Saavedra, Héctor Hernando
title A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_short A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_full A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_fullStr A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_full_unstemmed A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_sort new zwitterionic, water soluble, re(i) complex: synthesis, spectroscopic and computational characterization
publishDate 2013
url http://sedici.unlp.edu.ar/handle/10915/151450
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