Ab initio paramagnetic NMR shifts via point-dipole approximation in a large magnetic-anisotropy Co(ii) complex

Physical Chemistry Chemical Physics : PCCP
Jiří Mareš, Juha Vaara

Abstract

Transition metal complexes can possess a large magnetic susceptibility anisotropy, facilitating applications such as paramagnetic tags or shift agents in nuclear magnetic resonance (NMR) spectroscopy. Due to its g-shift and zero-field splitting (ZFS) we demonstrate on a Co(ii) clathrochelate with an aliphatic 16-carbon chain, a modern approach for ab initio calculation of paramagnetic susceptibility. Due to its large anisotropy, large linear dimension but relatively low number of atoms, the chosen complex is especially well-suited for testing the long-range point-dipole approximation (PDA) for the pseudocontact shifts (PCSs) of paramagnetic NMR. A static structure of the complex is used to compare the limiting long-distance PDA with full first-principles quantum-mechanical calculation. A non-symmetric formula for the magnetic susceptibility tensor is necessary to be consistent with the latter. Comparison with experimental shifts is performed by conformational averaging over the chain dynamics using Monte Carlo simulation. We observe satisfactory accuracy from the rudimentary simulation and, more importantly, demonstrate the fast applicability of the ab initio PDA.

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Citations

Apr 15, 2019·The Journal of Chemical Physics·Giacomo ParigiClaudio Luchinat
Jun 11, 2019·The Journal of Physical Chemistry Letters·Linda CerofoliniClaudio Luchinat
Jan 7, 2022·Dalton Transactions : an International Journal of Inorganic Chemistry·Paulo Pérez-LouridoLaura Valencia

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Methods Mentioned

BETA
NMR
electron paramagnetic resonance

Software Mentioned

NEVPT2
Turbomole
Orca

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