Size-Dependent Ligand Quenching of Ferromagnetism in Co 3 (benzene) n + Clusters Studied with X-ray Magnetic Circular Dichroism Spectroscopy
Cobalt–benzene cluster ions of the form Co 3 (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. Co 3 + has a spin magnetic moment of μS = 6 μB and an orbital magnetic moment of μL = 3 μB. Co 3 (bz) + and Co 3 (bz) 2 + complexes were found to have spin and orbital magnetic moments identical to the values for ligand-free Co 3 + . However, coordination of the third benzene to form Co 3 (bz) 3 + completely quenches the high spin state of the system. Density functional theory calculations elucidate the spin states of the Co 3 (bz) n + species as a function of the number of attached benzene ligands, explaining the transition from septet to singlet for n = 0 → 3.