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

项目结束后，我们就以下主题开展了工作。1)吡啶磺酸盐空间结构的分类与控制。2)大环多吡啶的研究进展及配合物的形成。3)利用三吡啶硫代甲烷构建新型Cu（II）-C（sp^3）键。4)吡啶硫代铜原子簇发光现象的探讨。吡啶磺酸盐复合物通过共价排列或通过氢和p-p相互作用形成1维和2维复合聚合物而形成多功能聚合物结构。吡啶和硫的结合可以形成有趣的大环结构，硫杂杯[3]吡啶。利用该配体，我们发现了第一例大环多吡啶配合物。铜的配合物通过Cu-S键通过补偿键形成二聚体结构，作为进一步与各种配体配位的起始原料。结果表明，配合物具有有趣的发光行为，并与各种芳香体系相互作用。吡啶硫醇的C-S键显示出有趣的反应性，从元素硫的消除开始，并形成甜菜碱，吡啶吡啶鎓，作为结果。在此反应之后，已经合成了双-吡啶基硫代甲烷和三-吡啶基硫代甲烷。后一种配体与吡啶和去质子化甲烷作为三脚架配体。我们发现了Cu（II）-C（sp^3）键的第一个例子，并探讨了该配合物的反应活性。该键形成的配位反应需要Cu（I）金属源和分子氧，这表明存在含氧去质子化。这些多功能现象的本质是刚性吡啶与柔性硫和柔性硫的互补作用。

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.