Constructing Highly Conducting Metal−Metal Bonded Solids by Electrocrystallization of [PtII2(RCS2)4] (RCS2− = Dithiocarbox
详细信息 查看全文
- 作者：Minoru Mitsumi ; Hidekazu Ueda ; Kazumi Furukawa ; Yoshiki Ozawa ; Koshiro Toriumi ; Mohamedally Kurmoo
- 刊名：Journal of the American Chemical Society
- 出版年：2008
- 出版时间：October 29, 2008
- 年：2008
- 卷：130
- 期：43
- 页码：14102-14104
- 全文大小：305K
- 年卷期：v.130,no.43(October 29, 2008)
- ISSN：1520-5126
文摘
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 × 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.