Multi-nuclear Polymeric Complex bridged Isonitriles

在这项研究中的目的是取代氰化物配位体的混合价多核金属配合物具有特定的电，磁，和光学性能的功能异腈配位体，有可能提供另一个功能。在本财政年度，在具有高导电性的一维铂络合物的单晶上的分子排列的结构相变。(1)用原子力显微镜（AFM）记录了电化学制备的溴化四氰铂酸钾（KCP（Br））单晶在针尖诱导表面修饰过程中的分子分辨率图像。KCP（Br）晶体（010）面上的两种分子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K^+、Br^-离子的分子排列方式一致 ...更多信息 结果与X射线衍射法一致。另一个对应于重排的间隙离子（K^+和Br^-）layr。(2)利用原子力显微镜（AFM）获得的分子分辨率图像揭示了溴化四氰铂酸钾（KCP（Br））单晶在脱水和水化处理过程中（010）面上分子排列的可逆有序-无序转变。脱水晶体中沿着c轴的柱内Pt-Pt间距增加了30%，并出现了相当程度的无序，再水化晶体与生长态晶体一样呈现良好的有序排列，而沿着正交方向的柱间结构没有变化。大尺度AFM图像显示，在脱水-水化处理过程中，单层梯田沿c轴方向可逆滑动，反映了分子沿着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非常一致，即，晶格无序和电导率降低。少

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