Magnetic Anisotropy of Homo- and Heteronuclear Terbium(III) and Dysprosium(III) Trisphthalocyaninates Derived from Paramagnetic <sup>1</sup>H-NMR Investigation
Ilya D. Kormschikov,
Marina A. Polovkova,
Gayane A. Kirakosyan,
Alexander G. Martynov,
Yulia G. Gorbunova,
Aslan Yu. Tsivadze
Affiliations
Ilya D. Kormschikov
Faculty of Chemistry, Lomonosov Moscow State University, GSP-1, Leninskie Gory, 119991 Moscow, Russia
Marina A. Polovkova
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr., 31, Building 4, 119071 Moscow, Russia
Gayane A. Kirakosyan
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr., 31, Building 4, 119071 Moscow, Russia
Alexander G. Martynov
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr., 31, Building 4, 119071 Moscow, Russia
Yulia G. Gorbunova
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr., 31, Building 4, 119071 Moscow, Russia
Aslan Yu. Tsivadze
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr., 31, Building 4, 119071 Moscow, Russia
1H-NMR spectroscopy of lanthanide complexes is a powerful tool for deriving spectral–structural correlations, which provide a clear link between the symmetry of the coordination environment of paramagnetic metal centers and their magnetic properties. In this work, we have first synthesized a series of homo- (M = M* = Dy) and heteronuclear (M ≠ M* = Dy/Y and Dy/Tb) triple-decker complexes [(BuO)8Pc]M[(BuO)8Pc]M*[(15C5)4Pc], where BuO- and 15C5- are, respectively, butoxy and 15-crown-5 substituents on phthalocyanine (Pc) ligands. We provide an algorithmic approach to assigning the 1H-NMR spectra of these complexes and extracting the axial component of the magnetic susceptibility tensor, χax. We show how this term is related to the nature of the lanthanide ion and the shape of its coordination polyhedron, providing an experimental basis for further theoretical interpretation of the revealed correlations.
