Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry

Quantum mechanical calculations at the density functional theory (DFT) level have been performed on diruthenium tetracarboxylates of different levels of molecular complexity: from unsolvated monomers to oligomers. The agreement between the calculated and experimental molecular structures and vibrati...

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Publicado: 2008
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v47_n11_p4682_Castro
http://hdl.handle.net/20.500.12110/paper_00201669_v47_n11_p4682_Castro
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_00201669_v47_n11_p4682_Castro2023-06-08T14:40:35Z Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry Quantum mechanical calculations at the density functional theory (DFT) level have been performed on diruthenium tetracarboxylates of different levels of molecular complexity: from unsolvated monomers to oligomers. The agreement between the calculated and experimental molecular structures and vibrational modes of the simple [Ru 2 (μ-O 2 CCH 3 ) 4 ] 0/ +and [Ru 2 (μ-O 2 CCH 3 ) 4 (H 2 O) 2 ] 10/+ systems made us confident in our calculation methodology. Therefore, it has been applied to the analysis of two different kinds of properties of these compounds: the trends in the UV/vis spectroscopy and electrochemistry along the [Ru 2 (μ-O 2 CCH 3 ) 4 X 2 ] - (X = Cl - , Br - , I) series, and the crystalline polymorphism related to the polymeric strand conformation in extended Ru 2 (μ-O 2 CR) 4 Cl compounds. For the [Ru 2 (μ-O 2 CCH 3 ) 4 X 2 ] - series, we report new spectroscopic and electrochemical results and interpret the trends on the basis of time dependent DFT-polarized continuum model calculations, local charge and spin analysis, and X donor properties. As far as the polymeric conformation is concerned, it has been previously suggested that the Ru-Cl-Ru angle results from a compromise between packing, orbital overlap, and microsegregation. Our calculations on [RU 2 (μ-O 2 CCH 3 ) 4 Cl] 2 Cl - and [Ru 2 (μ-O 2 CCH 3 ) 4 Cl] 3 Cl - oligomers provide insights on the influence of the first two factors on the strand conformation and allows a suggestion on what is the equatorial aliphatic chain's influence on this issue. © 2008 American Chemical Society. 2008 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v47_n11_p4682_Castro http://hdl.handle.net/20.500.12110/paper_00201669_v47_n11_p4682_Castro
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description Quantum mechanical calculations at the density functional theory (DFT) level have been performed on diruthenium tetracarboxylates of different levels of molecular complexity: from unsolvated monomers to oligomers. The agreement between the calculated and experimental molecular structures and vibrational modes of the simple [Ru 2 (μ-O 2 CCH 3 ) 4 ] 0/ +and [Ru 2 (μ-O 2 CCH 3 ) 4 (H 2 O) 2 ] 10/+ systems made us confident in our calculation methodology. Therefore, it has been applied to the analysis of two different kinds of properties of these compounds: the trends in the UV/vis spectroscopy and electrochemistry along the [Ru 2 (μ-O 2 CCH 3 ) 4 X 2 ] - (X = Cl - , Br - , I) series, and the crystalline polymorphism related to the polymeric strand conformation in extended Ru 2 (μ-O 2 CR) 4 Cl compounds. For the [Ru 2 (μ-O 2 CCH 3 ) 4 X 2 ] - series, we report new spectroscopic and electrochemical results and interpret the trends on the basis of time dependent DFT-polarized continuum model calculations, local charge and spin analysis, and X donor properties. As far as the polymeric conformation is concerned, it has been previously suggested that the Ru-Cl-Ru angle results from a compromise between packing, orbital overlap, and microsegregation. Our calculations on [RU 2 (μ-O 2 CCH 3 ) 4 Cl] 2 Cl - and [Ru 2 (μ-O 2 CCH 3 ) 4 Cl] 3 Cl - oligomers provide insights on the influence of the first two factors on the strand conformation and allows a suggestion on what is the equatorial aliphatic chain's influence on this issue. © 2008 American Chemical Society.
title Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
spellingShingle Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
title_short Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
title_full Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
title_fullStr Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
title_full_unstemmed Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
title_sort theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
publishDate 2008
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v47_n11_p4682_Castro
http://hdl.handle.net/20.500.12110/paper_00201669_v47_n11_p4682_Castro
_version_ 1768544486867075072

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