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

Kavipriya Thangavel; Paolo Cleto Bruzzese; Matthias Mendt; Andrea Folli; Katharina Knippen; Dirk Volkmer; Damien M. Murphy; Andreas Pöppl

doi:10.1039/D3CP01449E

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

Kavipriya Thangavel,

‡^ab Paolo Cleto Bruzzese,

‡§^ac Matthias Mendt,¶^a Andrea Folli,

^b Katharina Knippen,^d Dirk Volkmer,

^d Damien M. Murphy

^b and Andreas Pöppl

*^a

Author affiliations

* Corresponding authors

^a Felix Bloch Institute for Solid State Physics, Leipzig University, Linnéstraße 5, 04103 Leipzig, Germany
E-mail: poeppl@physik.uni-leipzig.de

^b School of Chemistry, Main building, Cardiff University, Cardiff, UK

^c Department of Chemistry and NIS Centre of Excellence, University of Turin, via Giuria 9, 10125 Torino, Italy

^d Institute of Physics, Chair of Solid State and Materials Chemistry, University of Augsburg, Universitätstraße 1, D-86159 Augsburg, Germany

Abstract

The nature of the chemical bonding between NO and open-shell Ni^II 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 Ni^II 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 Ni^II–NO species and retrieving their microscopic structure.

This article is part of the themed collection: 2023 PCCP HOT Articles

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Article information

DOI: https://doi.org/10.1039/D3CP01449E
Article type: Paper
Submitted: 30 Mar 2023
Accepted: 20 May 2023
First published: 22 May 2023
This article is Open Access

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Phys. Chem. Chem. Phys., 2023,25, 15702-15714

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

K. Thangavel, P. C. Bruzzese, M. Mendt, A. Folli, K. Knippen, D. Volkmer, D. M. Murphy and A. Pöppl, Phys. Chem. Chem. Phys., 2023, 25, 15702 DOI: 10.1039/D3CP01449E

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