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Neutral gold and nickel bis[1-(pyridin-4-yl)-ethylene-1,2-dithiolene] complexes: Synthesis, structure and physical properties

Rabaça, S. ; Cerdeira, A. ; Oliveira, S.O. ; Santos, I. C. ; Henriques, R. T. ; Pereira, L. ; Coutinho, J.T.C. ; Almeida, M.

Polyhedron Vol. 39, Nº 1, pp. 91 - 98, May, 2012.

ISSN (print): 0277-5387
ISSN (online):

Journal Impact Factor: 1,801 (in 2008)

Digital Object Identifier: 10.1016/j.poly.2012.03.024

The Ni and Au bis(dithiolene) complexes based on the 1-(pyridine-4-yl)-ethylene-1,2-dithiolate ligand were prepared in their neutral state and characterized namely by single-crystal X-ray diffraction, electronic UV–Vis–NIR spectroscopy, EPR and magnetic susceptibility measurements. The crystal structure of the neutral complex [Ni(4-pedt)2]0 lacks a regular and multidimensional extended network of short contacts and as a consequence electrical conductivity measurements in single crystals show a semiconducting behavior with room temperature values of the order of 10−6 S/cm, while the magnetic measurements of the gold compounds indicate a reduced effective magnetic moment due to strong antiferromagnetic interactions between radical neutral complex units. The nitrogen coordination ability of theses complexes was demonstrated by the coordination of pyridine to a sodium ion observed in the [Au(4-pedt)2]2NaPF6 complex which was also characterized by single-crystal X-ray diffraction and magnetization. In this compound the Na ions in half occupied positions are coordinated by anion fluorine atoms and nitrogen and carbon atoms from the neutral [Au(4-pedt)2] complexes.