Unveiling the atomistic and electronic structure of Ni II –NO adduct in a MOF-based catalyst by EPR spectroscopy and quantum chemical modelling †

Thangavel, Kavipriya, Bruzzese, Paolo Cleto, Mendt, Matthias, Folli, Andrea ORCID: https://orcid.org/0000-0001-8913-6606, Knippen, Katharina, Volkmer, Dirk, Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879 and Pöppl, Andreas 2023. Unveiling the atomistic and electronic structure of Ni II –NO adduct in a MOF-based catalyst by EPR spectroscopy and quantum chemical modelling †. Physical Chemistry Chemical Physics 10.1039/d3cp01449e

PDF - Published Version Available under License Creative Commons Attribution. Download (1MB)

Abstract

The nature of the chemical bonding between NO and open-shell NiII ions docked in a metal–organic framework is fully characterized by EPR spectroscopy and computational methods. High-frequency EPR experiments reveal the presence of unsaturated NiII ions displaying five-fold coordination. Upon NO adsorption, in conjunction with advanced EPR methodologies and DFT/CASSCF modelling, the covalency of the metal–NO and metal–framework bonds is directly quantified. This enables unravelling the complex electronic structure of NiII–NO species and retrieving their microscopic structure.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Chemistry
Additional Information:	License information from Publisher: LICENSE 1: URL: http://creativecommons.org/licenses/by/3.0/, Start Date: 2023-05-22
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Date of First Compliant Deposit:	2 June 2023
Date of Acceptance:	20 May 2023
Last Modified:	03 Jun 2023 07:24
URI:	https://orca.cardiff.ac.uk/id/eprint/160119

Actions (repository staff only)

Edit Item