Article

Electrical properties and electronic states of molecular conductors based on unsymmetrical organometallic-dithiolene gold(III) complexes.

RIKEN, JST-CREST, 2-1, Hirosawa, Wako-shi, Saitama 351-0198, Japan.
Inorganic Chemistry (impact factor: 4.6). 07/2008; 47(12):5495-502. DOI:10.1021/ic800176q pp.5495-502
Source: PubMed

ABSTRACT The electronic properties of cation radical salts derived from organometallic mixed-ligand complexes [(ppy)Au(S-S)](ppy- = C-dehydro-2-phenylpyridine(-); S-S(2-) = dithiolene ligand) with Au(III)-C sigma-bond were investigated. A 2:1 salt complex [(ppy)Au(C8H4S8)]2[PF6] (C8H4S8(2-) = 2-((4,5-ethylenedithio)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) exhibited semiconductive behavior under ambient pressure (rho rt = 2.6 Omega cm, Ea = 0.03 eV). Magnetic measurements show that it is a Mott insulator close to the metal-insulator boundary. Raman and infrared spectra have revealed that the complex has a quasi-one-dimensional dimeric structure consisting of uniformly charged donor molecules. The complex exhibits metallic behavior at pressures above 0.8 GPa. In contrast, a similar compound [(ppy)Au(C8H4S6O2)]2[BF4] (C8H4S6O2(2-) = 2-((4,5-ethylenedioxy)-1,3-dithiole-2-ylidene)-1,3-dithiole-4,5-dithiolate(2-)) is a band insulator.

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Keywords

ambient pressure
 
Au(III)-C sigma-bond
 
band insulator
 
cation radical salts
 
donor molecules
 
electronic properties
 
infrared spectra
 
metal-insulator boundary
 
Mott insulator
 
pressures
 
quasi-one-dimensional dimeric structure