Abstract
The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the two quinone-based derivatives 4,7-di-tert-butyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)benzo[d][1,3]dithiole-5,6-dione (L1) and 7,8-dithiabicyclo[4.2.0]octa-1,5-diene-3,4-dione,2,5bis(1,1-dimethylethyl) (L2) led respectively to the complexes [Dy(hfac)3(H2O)(L1)] (1) and [Dy(hfac)3(H2O) (L2)]⋅(C6H14)(CH2Cl2) (2)⋅(C6H14)(CH2Cl2). X-ray structures on single crystal of 1 and 2⋅(C6H14)(CH2Cl2) revealed the coordination of the DyIII on the bischelating oxygenated quinone site and the formation of dimeric species through hydrogen bonds. Ac magnetic measurements highlighted field-induced single-molecule magnet behavior with magnetic relaxation through a Raman process.
Highlights
Konstantin Martyanov 1, Jessica Flores Gonzalez 2, Sergey Norkov 1, Bertrand Lefeuvre 2, Vincent Dorcet 2, Vladimir Cherkasov 1, Olivier Cador 2, Viacheslav Kuropatov 1, * and Fabrice Pointillart 2, *
The design of the coordination surrounding of magneto-active ions is a challenging task; a choice of o-quinone-like dioxolenes for this purpose seems to be promising for several reasons: (i) o-dioxolenes possess a redox activity, their oxidation state may be changed directly in the coordination sphere of the metal ion [1,2,3]
It is worth mentioning that single-molecule magnet (SMM) behavior is associated to the observation of slow magnetic relaxation at the molecular scale, leading to the opening of a hysteresis loop at low temperature
Summary
Konstantin Martyanov 1 , Jessica Flores Gonzalez 2 , Sergey Norkov 1 , Bertrand Lefeuvre 2 , Vincent Dorcet 2 , Vladimir Cherkasov 1 , Olivier Cador 2 , Viacheslav Kuropatov 1, * and Fabrice Pointillart 2, *. The recent discovery of organometallic complexes of dysprosium with high blocking temperature [21,22,23,24] make them potential candidates for high density data storage; (ii) due to chelating ability, o-dioxolenes form stable complexes with almost all metals; (iii) o-quinone may be modified with various additional redox-active, free radical bearing or coordination-capable functional fragments to provide possibilities for the switching of the redox and/or magnetic state of the molecule [25]. The interest for metal dithiolenes emerged due to their potential applications in molecular conductors and superconductors [26] They have been recently employed to study electronic spin decoherence for quantum computation [27,28,29]
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