Jump to main content
Jump to site search

Issue 35, 2018
Previous Article Next Article

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

Author affiliations

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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 29 Jun 2018, accepted on 15 Aug 2018 and first published on 20 Aug 2018


Article type: Paper
DOI: 10.1039/C8CP04123G
Citation: Phys. Chem. Chem. Phys., 2018,20, 22547-22555
  • Open access: Creative Commons BY license
  •   Request permissions

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

    J. Mareš and J. Vaara, Phys. Chem. Chem. Phys., 2018, 20, 22547
    DOI: 10.1039/C8CP04123G

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements