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Fluorine Segregation Controls the Solid‐State Organization and Electronic Properties of Ni and Au Dithiolene Complexes: Stabilization of a Conducting Single‐Component Gold Dithiolene Complex
Author(s) -
Dautel O.J.,
Fourmigué M.,
Canadell E.,
AubanSenzier P.
Publication year - 2002
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/1616-3028(20021016)12:10<693::aid-adfm693>3.0.co;2-f
Subject(s) - isostructural , materials science , tetrathiafulvalene , conductivity , nickel , metal , salt (chemistry) , semiconductor , fluorine , crystallography , chemistry , molecule , crystal structure , organic chemistry , metallurgy , optoelectronics
Electrooxidation of the nickel dithiolene complex [Ni(F 2 pdt) 2 ] –· (F 2 pdt 2‐ : 6,6‐difluoro‐6,7‐dihydro‐5 H ‐[1,4]dithiepine‐2,3‐dithiolato) affords the corresponding neutral complex [Ni(F 2 pdt) 2 ] 0 whose layered structure is highly reminiscent, albeit not isostructural, of that of the isosteric fluorinated bis(propylenedithio)tetrathiafulvalene and characterized by a segregation of the fluorinated moieties into fluorous bilayers. The gold neutral complex [Au(F 2 pdt) 2 ] · , which is isostructural with the fluorinated bis(propylenedithio)tetrathiafulvalene, was prepared by electrocrystallization of the [ n ‐Bu 4 N][Au(F 2 pdt) 2 ] salt. [Au(F 2 ‐pdt) 2 ] · is a semiconductor with high room temperature conductivity. The origin of this semiconducting behavior as well as possible guidelines in order to realize metallic conductivity in gold dithiolene neutral molecular solids are discussed.