Development of Multi-functional Ligands for Application of Metal Complexes

1.为了获得其中八面体配合物作为侧链的低聚物或聚合物，已经研究了Co（III）-DHPTA单核配合物的酰化，其中DHPTA代表1，3-二氨基-2-羟基丙烷-N，N，N ′，N ′-四乙酸。配合物中的非配位羟基基团成功地甲基丙烯酸酯化的反应，相应的酸酐与配合物在非质子溶剂中，只有在穴状配体的存在下。在阻聚剂存在下，引入一个可聚合的甲基丙烯酰基。另一方面，在没有阻聚剂的情况下，络合物的甲基丙烯酸酯化产物可以在酰化后通过顺序聚合形成水凝胶。该结果表明，在化学改性中获得了多配体低聚物或聚合物。我们现在正在研究利用这里得到的水凝胶作为一种应用而获得陶瓷薄膜的可能性。大气中氮氧化物的去除不仅是化学领域的重要课题，也是环境科学研究的重要内容.在本项目中，我们研究了在上述多功能配体DHPTA存在下，亚硝酸根离子与铁（III）的配位行为。通过对一个绿色化合物的X-射线晶体结构测定，我们发现了一个含有两个桥联亚硝酸根离子的μ-氧代四核Fe（III）配合物离子的形成。这一结果表明，由铁（III）和DHPTA的反应体系可能提供了一个机会，从严重的酸雨氮氧化物的捕获和去除。此外，这类新型的四核配合物在生物化学和磁学领域都有着广泛的应用前景。

1. The acylation of a Co(III)-DHPTA mononuclear complex have been examined in order to obtain oligomers or polymers in which an octahedral complex are as the side chain, where DHPTA represents 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid. The non-coordinated hydroxyl group in the complex was successfully methacrylated by the reaction of the corresponding acid anhydride with the complex in aprotic solvent, only in the presence of a cryptand. In the presence of a polymerization inhibitor, one methacryl group which can be polymerized, was introduced. On the other hand, the products, which may be formed by sequential polymerization after the acylation, from the methacrylation of the complex without polymerization inhibitor, gave a hydro-gel. This result indicates that the multi-ligand oligomer or polymer is obtained in the chemical modification. We are now examininig the possibility to obtain films of ceramics by the use of hydro-gel obtained here, as an application.2. Removal of Nitrogen oxides in atmosphere is an important subject, not only for chemistry. In this project, we have investigated the coordination behaviors of nitrite ion toward iron(III) in the presence of the above multi-functional ligand, DHPTA. We found the formation of mu -oxo tetranuclear Fe(III) complex ion involving two bridging nitrite ions, from the X-ray crystal structure determination of an isolated green compound Significantly, the multinuclear complex was discovered from an acidic aqueous solution, pH below 2.5. This result suggests that the reaction system consisted of iron(III) and DHPTA may afford an opportunity for capture of nitrogen oxides from serious acid rain and their removal. Moreover, the novel tetranuclear complex are interested in both fields of biochemistry and magnetochemistry.