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Multi-nuclear Polymeric Complex bridged Isonitriles

多核聚合物配合物桥联异腈

基本信息

批准号：
08455400
负责人：
IYODA Tomokazu
金额：
$ 4.86万
依托单位：
TOKYO METROPOLITAN UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

项目摘要

The objective in this study is to replace cyanide ligands of mixed valence polynuclear metal complexes with specific electric, magnetic, and optical properties by functional isonitrile ligands which have potential to provide another functionality. In this fiscal year, structural phase transition of molecular arrangement on a single crystal of one-dimensional platinum complex with high electric conductivity.(1) Molecular-resolution images of an electrochemically prepared single crystal of potassium tetracyanoplatinate bromide complex (KCP(Br)) were recorded by atomic force microscopy (AFM) during a tip-induced surface modification process in which the probing tip scraped off the topmost surface layr by layr. Two kinds of molecular images on the (010) face of the KCP(Br) crystal correspond to alternate layred structures consisting of tetracyanoplatinate layrs and interstitial ions. One molecular arrangement was assigned to cyanide ligands and interstitial K^+ and Br^- ions, in good agree … More ment with that obtained from X-ray diffraction. The other corresponds to rearranged interstitial ion (K^+ and Br^-) layr.(2) Molecular-resolution images by atomic force microscopy (AFM) revealed reversible ordering-disordering transition of molecular arrangements on the (010) face of a single crystal of potassium tetracyanoplatinate bromide (KCP(Br)) during dehydration and hydration treatments. The intracolumnar Pt-Pt distance along c-axis in the dehydrated crystal lengthens by a factor of 30% with considerable disordering, and the re-hydrated crystal shows well-ordered arrangement like the as-grown crystal, while the intercolumnar structures along the orthogonal direction is not varied. In large-scale AFM images showed that the monolayr terraces reversibly slides in the c-axis direction during the dehydration-hydration treatments, reflecting the molecular dislocation along c-axis. These surface structural change is quite consistent with well-known dehydration effect in KCP(Br) crystal, i.e., the lattice disordering and the decreasing conductivity. Less

本研究的目的是用具有其他功能的异腈配体取代具有特定电、磁和光学性质的混合价多核金属配合物的氰化物配体。本财政年度研究了具有高导电性的一维铂配合物单晶上分子排列的结构相变。(1)利用原子力显微镜（AFM）记录了电化学制备的四氰铂酸钾溴化络合物（KCP(Br)）单晶在探针尖诱导表面修饰过程中的分子分辨率图像，探针尖逐层刮去最上层的表面。KCP（Br）晶体（010）表面的两种分子图像对应于由四氰铂酸盐层和间隙离子组成的交替层状结构。氰化物配体和间隙的K^+和Br^-离子有一个分子排列，与x射线衍射结果一致。另一个对应于重排的间隙离子层（K^+和Br^-）。(2)原子力显微镜（AFM）的分子分辨率图像显示，在脱水和水化处理过程中，四氰铂基溴化钾（KCP(Br)）单晶（010）表面的分子排列发生了可逆的有序-无序转变。脱水晶体中柱内Pt-Pt沿c轴的距离增加了30%，且有明显的无序性，再水化晶体与生长晶体一样排列有序，而柱间沿正交方向的结构没有变化。大尺度AFM图像显示，在脱水-水合作用过程中，单层阶地沿c轴方向可逆滑动，反映了分子沿c轴的位错。这些表面结构变化与KCP（Br）晶体中众所周知的脱水效应（即晶格无序和电导率下降）非常一致。少