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 editorsCollins, Richard; José Heras Ojea, Maria; Mansikkamäki, Akseli; Tang, Jinkui; Layfield, Richard A.

Journal or seriesInorganic Chemistry

ISSN0020-1669

eISSN1520-510X

Publication year2020

Volume59

Issue number1

Pages range642-647

PublisherAmerican Chemical Society

Publication countryUnited States

Publication languageEnglish

DOIhttps://doi.org/10.1021/acs.inorgchem.9b02895

Publication open accessNot open

Publication channel open access

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


Abstract

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 keywordsmolecular magnetism; single-molecule magnets


Contributing organizations


Ministry reportingYes

VIRTA submission year2020

JUFO rating2


Last updated on 2024-12-10 at 05:31