TY - JOUR
T1 - Electrocrystallization and characterization of phosphonium-based radical anion salts [MePh3P] [Pd(dmit)2]3 and [Ph4P] [Pd(dmit)2]3 (dmit = 1,3-dithiole-2-thione-4,5-dithiolate). Comparison with related Pd and Ni isologues
AU - Pullen, Anthony E.
AU - Faulmann, Christophe
AU - Liu, Hsiang Lin
AU - Tanner, D. B.
AU - Abboud, Khalil A.
AU - Reynolds, John R.
N1 - Funding Information:
This work was funded by grants from the Air Force Office of Scientific Research ( I=49620-96-1-0067 ) for work completed in the Chemistry Department and the National Science Foundation (DMR-94038q4) for work completed in the Physics Department at the University of Florida. We also acknowledge the National Science Foundation for funding the purchase of the X-ray equipment at the University of Florida.
PY - 1998/11/10
Y1 - 1998/11/10
N2 - The two new radical anion salts [MePh3P] [Pd(dmit)2]3 (1) (dmit = C3S52 = 1,3-dithiole-2-thione-4,5-dithiolate) and [Ph4P]-[Pd(dmit)2]3 (2) have been synthesized and characterized by X-ray diffraction, elemental analysis and temperature-dependent conductivity measurements. Complexes 1 and 2 were prepared via electrooxidation of [Pd(dmit)2]2- in acetonitrile-acetone solvent mixtures at a Pt wire anode in the presence of methyltriphenylphosphonium bromide and tetraphenylphosphonium bromide electrolytes, respectively. For [MePh3P] [Pd(dmit)2]3 (1), black shiny needle and platelet crystals suitable for X-ray analysis were obtained. The crystal packing structure consists of layers of Pd(dmit)2 units separated by layers of MePh3P+ counterions. The Pd(dmit)2 layers are composed of dimers of Pd(dmit)2 units as a result of strong Pd⋯Pd interactions. Extensive S⋯S nonbonding interdimer intera ctions are observed, with each dimer interacting with six other adjacent dimers. For [Ph4P] [Pd(dmit)2]3 (2), black shiny flat needles were harvested and th e stoichiometry confirmed by elemental analysis. Single-crystal temperature-dependent conductivity measurements show that 1 behaves as a semiconductor with a room-temperature conductivity of 13 S cm-1 and a thermal activation energy of 100 meV. Compound 2 also displays semiconducting behavior with a room-temperature conductivity of 0.8-1 S cm-1 and a thermal activation energy of 55 meV.
AB - The two new radical anion salts [MePh3P] [Pd(dmit)2]3 (1) (dmit = C3S52 = 1,3-dithiole-2-thione-4,5-dithiolate) and [Ph4P]-[Pd(dmit)2]3 (2) have been synthesized and characterized by X-ray diffraction, elemental analysis and temperature-dependent conductivity measurements. Complexes 1 and 2 were prepared via electrooxidation of [Pd(dmit)2]2- in acetonitrile-acetone solvent mixtures at a Pt wire anode in the presence of methyltriphenylphosphonium bromide and tetraphenylphosphonium bromide electrolytes, respectively. For [MePh3P] [Pd(dmit)2]3 (1), black shiny needle and platelet crystals suitable for X-ray analysis were obtained. The crystal packing structure consists of layers of Pd(dmit)2 units separated by layers of MePh3P+ counterions. The Pd(dmit)2 layers are composed of dimers of Pd(dmit)2 units as a result of strong Pd⋯Pd interactions. Extensive S⋯S nonbonding interdimer intera ctions are observed, with each dimer interacting with six other adjacent dimers. For [Ph4P] [Pd(dmit)2]3 (2), black shiny flat needles were harvested and th e stoichiometry confirmed by elemental analysis. Single-crystal temperature-dependent conductivity measurements show that 1 behaves as a semiconductor with a room-temperature conductivity of 13 S cm-1 and a thermal activation energy of 100 meV. Compound 2 also displays semiconducting behavior with a room-temperature conductivity of 0.8-1 S cm-1 and a thermal activation energy of 55 meV.
KW - Crystal structures
KW - Dithiolate complexes
KW - Electrocrystallization
KW - Palladium complexes
KW - Phosphonium complexes
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U2 - 10.1016/S0020-1693(98)00169-8
DO - 10.1016/S0020-1693(98)00169-8
M3 - Article
AN - SCOPUS:0001846748
SN - 0020-1693
VL - 282
SP - 90
EP - 95
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1
ER -