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.
Mitsumi
Minoru
M
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
Ueda
Hidekazu
H
Furukawa
Kazumi
K
Ozawa
Yoshiki
Y
Toriumi
Koshiro
K
Kurmoo
Mohamedally
M
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