Constructing highly conducting metal-metal bonded solids by electrocrystallization of [Pt(II)2(RCS2)4] (RCS2(-) = dithiocarboxylato, R = methyl or ethyl).
Partially oxidized one-dimensional (1D) Pt-Pt chain compounds [Pt2(MeCS2)4]4ClO4.5PhCN (1) and [Pt2(EtCS2)4]5(ClO4)2 (2) were synthesized by electrocrystallization of diplatinum(II,II) complexes from different solvents. 1 and 2 consist of 1D Pt-Pt chains of stacked Pt-Pt dimers with short interdimer S...S contacts. Depending on the number of ClO4- per dimer and their positions, 1 forms a regular stack of Pt-Pt dimers, whereas 2 forms pentamer of dimers in the 1D chain. 1 exhibits high electrical conductivity (4.2-8.0 S cm-1) at 300 K and metallic behavior above 125 K. 2 is a semiconductor. 1 exhibits almost temperature independent magnetic susceptibility (ca. 1.1 x 10-4 emu mol-1) which is attributed to Pauli paramagnetism, whereas the spin degree of freedom in 2 has been lost. Although the basic structures are closely related, they exhibited different solid-state properties that depend on the valence state of the platinum atoms and the periodicity within the 1D chain.
Department of Material Science, Graduate School of Material Science, University of Hyogo, 3-2-1 Kouto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan. mitsumi@sci.u-hyogo.ac.jp
Minoru
M
Mitsumi
Hidekazu
H
Ueda
Kazumi
K
Furukawa
Yoshiki
Y
Ozawa
Koshiro
K
Toriumi
Mohamedally
M
Kurmoo
D002264:Carboxylic Acids / Q000737:chemistry*; D003460:Crystallization; D004553:Electric Conductivity; D004563:Electrochemistry; D008958:Models, Molecular; D009944:Organoplatinum Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010984:Platinum / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013696:Temperature
D002264:Carboxylic Acids; D009944:Organoplatinum Compounds; D013438:Sulfhydryl Compounds; D010984:Platinum