Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters

Alex A. Fertig; S. M. Gulam Rabbani; Melissa D. Koch; William W. Brennessel; Pere Miro; Ellen M. Matson

doi:10.1039/d0nr09201k

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Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters

Journal article

Peer reviewed

Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters

Alex A. Fertig, S. M. Gulam Rabbani, Melissa D. Koch, William W. Brennessel, Pere Miro and Ellen M. Matson

Nanoscale, Vol.13(12), pp.6162-6173

03/28/2021

DOI: 10.1039/d0nr09201k

PMID: 33734254

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https://www.osti.gov/biblio/1771356View

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Abstract

We report a rare example of the direct alkylation of the surface of a plenary polyoxometalate cluster by leveraging the increased nucleophilicity of vanadium oxide assemblies. Addition of methyl trifluoromethylsulfonate (MeOTf) to the parent polyoxovanadate cluster, [V6O13(TRIOL(R))(2)](2-) (TRIOL = tris(hydroxymethyl)methane; R = Me, NO2) results in functionalisation of one or two bridging oxide ligands of the cluster core to generate [V6O12(OMe)(TRIOL(R))(2)](1-) and [V6O11(OMe)(2)(TRIOL(R))(2)](2-), respectively. Comparison of the electronic absorption spectra of the functionalised and unfunctionalised derivatives indicates the decreased overall charge of the complex results in a decrease in the energy required for ligand to metal charge transfer events to occur, while simultaneously mitigating the inductive effects imposed by the capping TRIOL ligand. Electrochemical analysis of the family of organofunctionalised polyoxovanadate clusters reveals the relationship of ligand environment and the redox properties of the cluster core: increased organofunctionalisation of the surface of the vanadium oxide assembly translates to anodic shifts in the reduction events of the Lindqvist ion. Overall, this work provides insight into the electronic effects induced upon atomically precise modifications to the surface structure of nanoscopic, redox-active metal oxide assemblies.

Chemistry

Chemistry, Multidisciplinary

Materials Science

Materials Science, Multidisciplinary

Nanoscience & Nanotechnology

Physical Sciences

Physics

Physics, Applied

Science & Technology

Science & Technology - Other Topics

Technology

Details

Title: Subtitle: Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters
Creators: Alex A. Fertig - University of Rochester
S. M. Gulam Rabbani - University of South Dakota
Melissa D. Koch - University of Rochester
William W. Brennessel - University of Rochester
Pere Miro - University of South Dakota
Ellen M. Matson - University of Rochester
Resource Type: Journal article
Publication Details: Nanoscale, Vol.13(12), pp.6162-6173
DOI: 10.1039/d0nr09201k
PMID: 33734254
NLM abbreviation: Nanoscale
ISSN: 2040-3364
eISSN: 2040-3372
Publisher: Royal Soc Chemistry
Number of pages: 12
Grant note: DOI: 10.13039/100000015, name: U.S. Department of Energy, award: DE-SC0002106; DOI: 10.13039/100000001, name: National Science Foundation, award: CHE-1900125, OAC-1626516
Language: English
Date published: 03/28/2021
Academic Unit: Chemistry
Record Identifier: 9984618507702771

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