title: Molecular Alloys of Neutral Gold/Nickel Dithiolene Complexes in Single-Component Semiconductors.
abstract: Control of band filling or doping of molecular (semi)conductors can be performed by substitutional insertion of molecules with a similar shape but a different electron count, with one more or one less electron. This strategy has been explored here within the semiconducting, single-component, radical gold dithiolene complex [AuOC4] bearing para-butoxyphenyl substituents. Alloying with the corresponding neutral nickel dithiolene complex [NiOC4] lacking one electron afforded a complete isostructural series [NiOC4]1-x[AuOC4]x, spanning the whole composition range from x = 0 to x = 1 by 0.1 increments, further characterized by X-ray diffraction and EDX analyses. Magnetic susceptibility data confirm the antiferromagnetic interactions between neighboring radical gold dithiolene complexes. The electrical conductivity increases exponentially with the x gold fraction, while the activation energy remains constant in the more conducting, gold-rich samples. This behavior is tentatively assigned to the tunneling barriers of variable width (with x) but of constant height, separating more conducting gold-rich segments. Comparison of redox potentials for the 1e(-) oxidation and reduction of both [NiOC4] and [AuOC4] dithiolene complexes indicates that the [NiOC4] nickel complex does not act as a dopant for the radical [AuOC4] complex.
authors.affiliation: †Institut des Sciences Chimiques de Rennes (ISCR), Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Kenny
authors.initials: K
authors.lastname: Mebrouk
authors.affiliation: ‡Laboratoire de Physique des Solides (LPS), Université Paris-Sud, UMR CNRS 8502, Bât. 510, 91405 Orsay, France.
authors.forename: Wafa
authors.initials: W
authors.lastname: Kaddour
authors.affiliation: ‡Laboratoire de Physique des Solides (LPS), Université Paris-Sud, UMR CNRS 8502, Bât. 510, 91405 Orsay, France.
authors.forename: Pascale
authors.initials: P
authors.lastname: Auban-Senzier
authors.affiliation: ‡Laboratoire de Physique des Solides (LPS), Université Paris-Sud, UMR CNRS 8502, Bât. 510, 91405 Orsay, France.
authors.forename: Claude
authors.initials: C
authors.lastname: Pasquier
authors.affiliation: †Institut des Sciences Chimiques de Rennes (ISCR), Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Jeannin
authors.affiliation: †Institut des Sciences Chimiques de Rennes (ISCR), Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Franck
authors.initials: F
authors.lastname: Camerel
authors.affiliation: †Institut des Sciences Chimiques de Rennes (ISCR), Université Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Marc
authors.initials: M
authors.lastname: Fourmigué