Multi-nuclear Polymeric Complex bridged Isonitriles

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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