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

吡啶磺酸盐配合物的组装控制及其发光-磁性

基本信息

批准号：
11440200
负责人：
KINOSHITA Isamu
金额：
$ 3.97万
依托单位：
Osaka City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

项目摘要

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.

项目期结束后，我们进行了以下课题的工作。1)吡啶磺酸盐的尺寸结构分类与控制。2)大环多吡啶的发展和络合物的形成。3)利用三吡啶硫甲烷构建新型Cu(II)-C（sp^3）键。4)吡啶硫代铜簇发光现象的探索。吡啶磺酸盐配合物通过共价阵列或通过氢与p-p相互作用形成一、二维络合聚合物形成多用途聚合物结构。吡啶与硫的结合可以形成有趣的大环结构，即噻吩环[3]吡啶。利用该配体，我们首次发现了大环多吡啶配合物。铜配合物通过Cu-S键补偿键形成二聚体结构，是与各种配体进一步配位的起始物质。因此，该复合物表现出有趣的发光行为，并与各种芳香体系相互作用。吡啶硫醇的C-S键表现出有趣的反应活性，从消除单质硫开始，形成甜菜，吡啶吡啶硫酮。在此反应之后，合成了双吡啶基硫甲烷和三吡啶基硫甲烷。后一种配体与吡啶和去质子化的甲烷起三脚架配体的作用。我们发现了Cu(II)-C（sp^3）键的第一个例子，并探索了该配合物的反应性。该键形成的配位反应既需要Cu(I)金属源，也需要双氧，表明存在氧化脱质子反应。这些多用途的现象本质上来自于刚性吡啶与软柔性硫的补偿操作。