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Syntheses, Crystal Structures, and Solid State Properties of Halogen-bridged mixed-valence siplatinum complexes PtィイD22ィエD2(RCSィイD22ィエD2)ィイD24ィエD2I

卤桥混合价西铂配合物 PtD22D2(RCSD22D2)D24D2I 的合成、晶体结构和固态性质

基本信息

批准号：
09440232
负责人：
TORIUMI Koshiro
金额：
$ 6.08万
依托单位：
Himeji Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

Halogen-bridged mixed-valence diplatinum complexes PtィイD22ィエD2(RCSィイD22ィエD2)ィイD24ィエD2I (R= CHィイD23ィエD2 (1), CィイD22ィエD2HィイD25ィエD2 (2), n-CィイD23ィエD2HィイD27ィエD2 (3), n-CィイD24ィエD2HィイD29ィエD2(4)) with linear chain structures of repeating units {-I-Pt-Pt-} are particular interest because they are possible to take a variety of valence ordering. The crystals of 1 which was first reported by Bellitto et al. exhibit anomalous electrical conducting behavior (T < 300K, semiconductor ; 300 K < T < 340 K, metallic). The variable temperature crystal structure analyses revealed dynamic disorder of the ligands.In order to elucidate the relation between the solid state behavior and the valence ordering of Pt atoms on the linear chain, the compounds 2 - 4 were synthesized and their crystal structure analyses and electrical conducting measurements were carried out. The M-I transitions were observed for 2 and 4.Since the crystal structure analyses provided only the averaged structures, we tried to measure the diffuse scattering corresponding to low-dimensional valence ordering of Pt atoms. Single crystal X-ray photographs of the compounds 1 and 2 were taken at variable temperatures by using the vacuum type X-ray camera and SPring-8. It was revealed that although the diffuse scattering corresponding to the valence alternation along the linear chain have been observed for 2 above 200 K (metallic state), but changed to the Bragg spots below 100 K (semiconductive state).

Halogen-bridged混合价diplatinum复合物PtィイD22摊位ィエD2 (RCSィイD22摊位ィエD2)ィイD24ィエD2I (R = CHィイc15ィエD2 (1), CィイD22摊位ィエD2HィイD25ィエD2 (2), Cィイc15ィエD2HィイD27ィエD2 (3), CィイD24ィエD2HィイD29ィエD2(4)直链结构的重复单位{-I-Pt-Pt -}是特别感兴趣,因为他们可以采用多种价订购。Bellitto等人首次报道的1晶体表现出异常的导电行为（T < 300K，半导体；300K < T < 340 K，金属）。变温晶体结构分析揭示了配体的动态无序性。为了阐明Pt原子在线性链上的价序与固态行为的关系，合成了化合物2 ~ 4，并对其晶体结构进行了分析和电导率测量。在第2和第4段观察到M-I跃迁。由于晶体结构分析只提供了平均结构，我们试图测量与铂原子的低维价序相对应的扩散散射。利用真空型x射线相机和SPring-8在变温度下对化合物1和2进行了单晶x射线照相。结果表明，虽然在200 K以上（金属态）存在与价态交替相对应的沿线性链的扩散散射，但在100 K以下（半导体态）则发生了布拉格斑点。