Field-induced mononuclear cobalt(ii) single-molecule magnet (SMM) based on a benzothiadiazole-ortho-vanillin ligand†
ab
Svitlana
Petrusenko,
b
Vladimir N.
Kokozay,
b
Thomas
Cauchy,
a
Francesc
Lloret,
c
Miguel
Julve,
c
Joan
Cano
*c
and
Narcis
Avarvari
*a
Abstract
A unique π-conjugated benzothiadiazole-ortho-vanillin ligand (HL), characterized by single crystal X-ray diffraction and DFT calculations, has been prepared by condensation between 4-amino-benzothiadiazole (BTD) and ortho-vanillin. Its reaction with cobalt(II) acetate afforded the complex of formula [CoL2]·CH2Cl2 (1), for which the coordination environment of the cobalt centre is a distorted octahedron and the ligand acts as a monoanionic tridentate NNO chelate in its phenolate form. Intermolecular π–π stacking interactions between the π-conjugated BTD units provide an antiferromagnetic coupling pathway, as indicated by the analysis of the dc magnetic measurements of a crystalline sample of the complex and supported by DFT type calculations. The static magnetic behaviour of 1 is analysed according to spin–orbit coupling and zero-field splitting models. Remarkably, the complex exhibits slow relaxation of the magnetization under dc applied magnetic fields being thus a new example of field-induced mononuclear single-molecule magnet (SMM).
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