Tetranuclear Lanthanide Complexes Containing a Hydrazone-type Ligand. Dysprosium [2 × 2] Gridlike Single-Molecule Magnet and Toroic

Alexey Gusev; Radovan Herchel; Ivan Nemec; Victor Shul'gin; Igor L Eremenko; Kostantin Lyssenko; Wolfgang Linert; Zdeněk Trávníček

doi:10.1021/acs.inorgchem.6b02449

Tetranuclear Lanthanide Complexes Containing a Hydrazone-type Ligand. Dysprosium [2 × 2] Gridlike Single-Molecule Magnet and Toroic

Inorg Chem. 2016 Dec 5;55(23):12470-12476. doi: 10.1021/acs.inorgchem.6b02449. Epub 2016 Nov 16.

Authors

Alexey Gusev¹, Radovan Herchel², Ivan Nemec², Victor Shul'gin¹, Igor L Eremenko, Kostantin Lyssenko, Wolfgang Linert³, Zdeněk Trávníček²

Affiliations

¹ General and Physical Chemistry Department, Crimean Federal University , Simferopol, Crimea.
² Department of Inorganic Chemistry, RCPTM, Faculty of Science, Palacký University , Olomouc, Czech Republic.
³ Institute of Applied Synthetic Chemistry, Vienna University of Technology , Vienna, Austria.

PMID: 27934424
DOI: 10.1021/acs.inorgchem.6b02449

Abstract

A multidentate hydrazone-type ligand (Z,Z)-bis(1-(pyridin-2-yl)-1-amino-methylidene)oxalohydrazide (H₂L) was utilized in the synthesis of three new isomorphous tetranuclear complexes of the general formula [Ln₄(HL)₄(H₂L)₂(NO₃)₄](NO₃)₄·4CH₃OH (Ln = Gd^III, 1, Tb^III, 2, Dy^III, 3) with the gridlike [2 × 2] topology. The analysis of the static magnetic data revealed weak anti-ferromagnetic interaction among lanthanide(III) atoms, whereas dynamic magnetic data led to the observation of the single-molecule magnet behavior in zero static magnetic field for the Dy₄ compound 3 with U_eff = 42.6 K and τ₀ = 1.50 × 10^-5 s. The theoretical CASSCF calculations supported also the presence of the net toroidal magnetic moment, which classifies compound 3 also as a single-molecule toroic.