Transition Ion Strikes Back: Large Magnetic Susceptibility Anisotropy in Cobalt(II) Clathrochelates.
Transition-metal complexes are rarely considered as paramagnetic tags for NMR spectroscopy due to them generally having relatively low magnetic anisotropy. Here we report cobalt(II) cage complexes with the largest (among the transition-metal complexes) axial anisotropy of magnetic susceptibility, reaching as high as 12.6 × 10(-32) m(3) at room temperature. This remarkable anisotropy, which results from an unusual trigonal prismatic geometry of the complexes and translates into large negative value of the zero-field splitting energy, is high enough to promote reliable paramagnetic pseudocontact shifts at the distance beyond 2 nm. Our finding paves the way toward the applications of cobalt(II) clathrochelates as future paramagnetic tags. Given the incredible stability and functionalization versatility of clathrochelates, the fine-tuning of the caging ligand may lead to new chemically stable mononuclear single-molecule magnets, for which magnetic anisotropy is of importance.
†Nesmeyanov Institute of Organoelement Compounds, RAS, Vavilova str. 28, 119991 Moscow, Russia.
Valentin V
VV
Novikov
†Nesmeyanov Institute of Organoelement Compounds, RAS, Vavilova str. 28, 119991 Moscow, Russia.
Alexander A
AA
Pavlov
†Nesmeyanov Institute of Organoelement Compounds, RAS, Vavilova str. 28, 119991 Moscow, Russia.
Alexander S
AS
Belov
†Nesmeyanov Institute of Organoelement Compounds, RAS, Vavilova str. 28, 119991 Moscow, Russia.
Anna V
AV
Vologzhanina
‡Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470 Mülheim an der Ruhr, Germany.
Anton
A
Savitsky
†Nesmeyanov Institute of Organoelement Compounds, RAS, Vavilova str. 28, 119991 Moscow, Russia.
Yan Z
YZ
Voloshin
EPR; clathrochelates; magnetic anisotropy; paramagnetic tags; transition metal complexes