Control of the assembly of pyridine sulofonate complexes and its luminescent-magnetic properties

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After the end of the project period, we have worked on the following subject. 1)The classification and control of dimensional structure of pyridinesulfonate. 2)Development and complex formation of macrocyclic polypyridine. 3)Construction of novel Cu(II)-C(sp^3) bond using trispyridinethiomethane. 4)Exploration of luminescent phenomena of pyridinethiolato cluster of copper. Pyridinesulfonate complexes form versatile polymer structure either through covalent array or through hydrogen and p-p interaction forming 1 and 2 dimensional complex polymer. The combination of pyridine and sulfur can form interesting macrocyclic structure, thiacalix[3]pyridine. Using the ligand, we have found the first example of maclocyclic polypyridine complex. The complex of copper forms dimer structure via compensate bonding through Cu-S linkage, act as the starting material for the further coordination with various ligand. As a result, the complex exhibit interesting luminescent behavior and interaction with various aromatic systems. The C-S bond of the pyridinethiol shows interesting reactivity starting from the elimination of the elemental sulfur and forms a betain, pyridine pyridiniumthione, as a result. Following to this reaction, bis-pyridylthiomethane, and tris-pyridylthiomethane have been synthesized. The latter ligand act as a tripod ligand with pyridines and a deprotonated methane. We have found the first example of Cu(II)-C(sp^3) bond and explore the reactivity of this complex. The coordination reaction of the formation of this bond requires both Cu(I) metal source and dioxygen that suggest the existence of oxygenated deprotonation. These versatile phenomena essentially come from the compensative operation of rigid pyridine with soft and flexible sulfur.