Amphiphilic paramagnetic neutral gold dithiolene complexes Article - Mars 2009

R. Perochon, L. Piekara-Sady, W. Jurga, R. Clerac, Marc Fourmigué

R. Perochon, L. Piekara-Sady, W. Jurga, R. Clerac, Marc Fourmigué, « Amphiphilic paramagnetic neutral gold dithiolene complexes  », Dalton Transactions, mars 2009, pp. 3052-3061. ISSN 1477-9226

Abstract

The sulfiding of benzils with P4S10 in 1,3-dimethyl 2-imidazolidinone (DMI) as solvent allows for a direct synthesis of neutral radical, gold dithiolene complexes based on 1,2-bis-(4-alkoxyphenyl) ethylene-1,2-dithiolate ligands with n-butyl, n-octyl and n-dodecyl chains. The three neutral and soluble complexes Au-OC4, Au-OC8 and Au-OC12 exhibit a near infrared (NIR) absorption band around 1.5 mm and EPR characteristics which confirm a strong delocalization of the spin density on the electron-rich dithiolene ligands. X-Ray crystal structures of Au-OC4 and Au-OC12 are compared with those of the corresponding nickel complexes. They are characterised by segregation of the alkyl chains into layered structures with a stacking of the radical complexes into alternated spin chains, confirmed by the temperature dependence of the magnetic susceptibility which attests for antiferromagnetic interactions and a singlet ground state. Observations under polarising microscope and DSC experiments do not reveal a thermotropic behaviour for Au-OC12

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