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Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters

[Image: see text] We present the post-synthetic modification of a polyoxovanadate-alkoxide (POV-alkoxide) cluster via the reactivity of its cationic form, [V(6)O(7)(OCH(3))(12)](1+), with water. This result indicates that cluster oxidation increases the lability of bridging methoxide ligands, afford...

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Autores principales: Marinho, Thompson V., Schreiber, Eric, Garwick, Rachel E., Brennessel, William W., Matson, Ellen M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10523436/
https://www.ncbi.nlm.nih.gov/pubmed/37712579
http://dx.doi.org/10.1021/acs.inorgchem.3c02314
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author Marinho, Thompson V.
Schreiber, Eric
Garwick, Rachel E.
Brennessel, William W.
Matson, Ellen M.
author_facet Marinho, Thompson V.
Schreiber, Eric
Garwick, Rachel E.
Brennessel, William W.
Matson, Ellen M.
author_sort Marinho, Thompson V.
collection PubMed
description [Image: see text] We present the post-synthetic modification of a polyoxovanadate-alkoxide (POV-alkoxide) cluster via the reactivity of its cationic form, [V(6)O(7)(OCH(3))(12)](1+), with water. This result indicates that cluster oxidation increases the lability of bridging methoxide ligands, affording a ligand exchange reaction that serves to compensate for the increased charge of the cluster core. This synthetic advance affords the isolation of a series of POV-alkoxide clusters with varying degrees of μ(2)–O(2–) ligands incorporated at the surface, namely, [V(6)O(8)(OCH(3))(11)], [V(6)O(9)(OCH(3))(10)], and [V(6)O(10)(OCH(3))(9)]. Characterization of the POV-alkoxide clusters is described; changes in the infrared and electronic absorption spectra are consistent with the oxidation of the cluster core. We also examine the consequences of ligand substitution on the redox properties of the series of POV-alkoxide clusters via cyclic voltammetry; decreased alkoxide ligand density translates to a cathodic shift of analogous redox events. Ligand substitution also increases comproportionation constants of the Lindqvist core, indicating electron exchange between vanadium centers is promoted in structures with greater numbers of μ(2)–O(2–) ligands.
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spelling pubmed-105234362023-09-28 Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters Marinho, Thompson V. Schreiber, Eric Garwick, Rachel E. Brennessel, William W. Matson, Ellen M. Inorg Chem [Image: see text] We present the post-synthetic modification of a polyoxovanadate-alkoxide (POV-alkoxide) cluster via the reactivity of its cationic form, [V(6)O(7)(OCH(3))(12)](1+), with water. This result indicates that cluster oxidation increases the lability of bridging methoxide ligands, affording a ligand exchange reaction that serves to compensate for the increased charge of the cluster core. This synthetic advance affords the isolation of a series of POV-alkoxide clusters with varying degrees of μ(2)–O(2–) ligands incorporated at the surface, namely, [V(6)O(8)(OCH(3))(11)], [V(6)O(9)(OCH(3))(10)], and [V(6)O(10)(OCH(3))(9)]. Characterization of the POV-alkoxide clusters is described; changes in the infrared and electronic absorption spectra are consistent with the oxidation of the cluster core. We also examine the consequences of ligand substitution on the redox properties of the series of POV-alkoxide clusters via cyclic voltammetry; decreased alkoxide ligand density translates to a cathodic shift of analogous redox events. Ligand substitution also increases comproportionation constants of the Lindqvist core, indicating electron exchange between vanadium centers is promoted in structures with greater numbers of μ(2)–O(2–) ligands. American Chemical Society 2023-09-15 /pmc/articles/PMC10523436/ /pubmed/37712579 http://dx.doi.org/10.1021/acs.inorgchem.3c02314 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Marinho, Thompson V.
Schreiber, Eric
Garwick, Rachel E.
Brennessel, William W.
Matson, Ellen M.
Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters
title Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters
title_full Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters
title_fullStr Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters
title_full_unstemmed Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters
title_short Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters
title_sort manipulating ligand density at the surface of polyoxovanadate-alkoxide clusters
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10523436/
https://www.ncbi.nlm.nih.gov/pubmed/37712579
http://dx.doi.org/10.1021/acs.inorgchem.3c02314
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