Size-Dependent Ligand Quenching of Ferromagnetism in Co3(benzene)n+ Clusters Studied with X-ray Magnetic Circular Dichroism Spectroscopy

Scott T. Akin, Vicente Zamudio-Bayer, Kaining Duanmu, Georg Leistner, Konstantin Hirsch, Christine Bülow, Arkadiusz Lawicki, Akira Terasaki, Bernd Von Issendorff, Donald G Truhlar, J. Tobias Lau, Michael A. Duncan

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Cobalt-benzene cluster ions of the form Co3(bz)n+ (n = 0-3) were produced in the gas phase, mass-selected, and cooled in a cryogenic ion trap held at 3-4 K. To explore ligand effects on cluster magnetic moments, these species were investigated with X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopy. XMCD spectra yield both the spin and orbital angular momenta of these clusters. Co3+ has a spin magnetic moment of μS = 6 μB and an orbital magnetic moment of μL = 3 μB. Co3(bz)+ and Co3(bz)2+ complexes were found to have spin and orbital magnetic moments identical to the values for ligand-free Co3+. However, coordination of the third benzene to form Co3(bz)3+ completely quenches the high spin state of the system. Density functional theory calculations elucidate the spin states of the Co3(bz)n+ species as a function of the number of attached benzene ligands, explaining the transition from septet to singlet for n = 0 → 3.

Original languageEnglish (US)
Pages (from-to)4568-4575
Number of pages8
JournalJournal of Physical Chemistry Letters
Issue number22
StatePublished - Nov 17 2016

Bibliographical note

Funding Information:
We gratefully acknowledge the generous support for this work from the Air Force Office of Scientific Research through Grant FA9550-15-1-0088 (M.A.D.)

Publisher Copyright:
© 2016 American Chemical Society.

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