A1 Journal article (refereed)
Carbonyl Back-Bonding Influencing the Rate of Quantum Tunnelling in a Dysprosium Metallocene Single-Molecule Magnet (2020)

Collins, R., José Heras Ojea, M., Mansikkamäki, A., Tang, J., & Layfield, R. A. (2020). Carbonyl Back-Bonding Influencing the Rate of Quantum Tunnelling in a Dysprosium Metallocene Single-Molecule Magnet. Inorganic Chemistry, 59(1), 642-647. https://doi.org/10.1021/acs.inorgchem.9b02895

JYU authors or editors

Publication details

All authors or editors: Collins, Richard; José Heras Ojea, Maria; Mansikkamäki, Akseli; Tang, Jinkui; Layfield, Richard A.

Journal or series: Inorganic Chemistry

ISSN: 0020-1669

eISSN: 1520-510X

Publication year: 2020

Volume: 59

Issue number: 1

Pages range: 642-647

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.inorgchem.9b02895

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/74488


The isocarbonyl-ligated metallocene coordination polymers [Cp*2M(μ-OC)W(Cp)(CO)(μ-CO)]∞ were synthesized with M = Gd (1, L = THF) and Dy (2, no L). In a zero direct-current field, the dysprosium version 2 was found to be a single-molecule magnet (SMM), with analysis of the dynamic magnetic susceptibility data revealing that the axial metallocene coordination environment leads to a large anisotropy barrier of 557(18) cm–1 and a fast quantum-tunnelling rate of ∼3.7 ms. Theoretical analysis of two truncated versions of 2, [Cp*2Dy{(μ-OC)W(Cp)(CO)2}2]− (2a), and [Cp*2Dy(OC)2]+ (2b), in which the effects of electron correlation outside the 4f orbital space were studied, revealed that tungsten-to-carbonyl back-donation plays an important role in determining the strength of the competing equatorial field at dysprosium and, hence, the dynamic magnetic properties. The finding that a classical organo-transition-metal bonding scenario can be used as an indirect way of tuning the rate of quantum tunnelling potentially provides an alternative chemical strategy for utilizing the fast magnetic relaxation properties of SMMs.

Free keywords: molecular magnetism; single-molecule magnets

Contributing organizations

Ministry reporting: Yes

Reporting Year: 2020

JUFO rating: 2

Last updated on 2021-07-07 at 21:36