Synthesis and Regulation of Multinueclear Metal Active Center inside the Cage-type Ligand Molecule

在这些研究中，我们致力于在笼型配体(L)中合理合成稳定的多核过渡金属簇，以开发新的人工酶分子活性金属位点，在不分解的情况下进行反应。在漆酶等多铜酶中，我们成功地合成了具有四选o_2还原位点基序的三铜配合物。在氩气气氛下，[Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4(1)作为水和二羟基结合的三铜（II）种，可以捕获各种阴离子。1还与大气中的二氧化碳反应，立即生成[Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4,(2)。此外，笼型配体L可应用于其他过渡金属离子，我们成功地合成了锰（II）、三钯（II）和钴（II）离子的簇型过渡金属配合物。在三锰配合物[Mn_3(L)(CO_3)(OCOCH_3)(CH_3OH)_3(ClO_4)] (ClO_4)(3)中，碳酸盐阴离子是由二氧化碳与前驱体水-二羟基结合的三锰（II）中心反应形成的，可能是人工出氧配合物的最佳候选物之一。此外，我们成功地构建了三钯配合物(5)，其结构与三铜配合物2几乎相同，我们将二氧化碳吸收到五的三钯核心中。在5中，客体分子与内部笼型配体非共价相互作用。即使在三钴（II）络合物的ram中，也观察到类似的阴离子捕获行为。其他三核配合物和更复杂的金属中心的构建也在它们的研究中得到了新的进展

In them studies, we worked on rational synthesis of stable multinuclear transition metal clusters in cage-type ligand (L) for development of new active metal sites of artificial enzyme molecules, processing reactions without their decomposition. At fast, we succeeded in synthesizing a tricopper complex with a motif of the four-election O_2-reduction site in multicopper enzymes such as Laccase. Under Ar atmosphere, [Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4 (1) was made as the aqua-and dihydroxo-binding tricopper (II) species, which can catpture various anions. 1 also reacted with atmospheric carbon dioxide to give [Cu^<II>_3L(OH)_2(H_2O)](ClO_4)_4, (2), immediately. Furthermore, the cage-type ligand, L, can be applied to other transition metal ions, and we succeeded in synthesizing the cluster-type transition metal complexes of manganese(II), tripalladium(II), and cobalt(II) ions. In the trimanganese complex, [Mn_3(L)(CO_3)(OCOCH_3)(CH_3OH)_3(ClO_4)] (ClO_4) (3) , it is considered that the carbonate anion was formed from carbon dioxygen reacted with the precursor, aqua-and dihydroxo-binding trimmganese(II) center, which may be one of the best candidates for an artificial oxygen-evolving complex. In addition, we succeeded in constructing tripalladium complex (5), having the almost same structure as that of tricopper complex 2, taking carbon dioxide inside the tripalladium core of 5. In 5, the guest molecule non-covalently interacted with the cage-type ligand inside. Even in ram of a tricobalt(II) complex, similar capturing behavior for anions were observed. Construction of the other trinuclear complexes and further complicated metal centers were also newly approached in them studies