Construction reaction of bowl-type vanadium oxide molecule by template reaction

金属氧化物是现代社会高科技领域的热门材料之一，如超导性、磁性或半导体性质、催化剂等。当我们寻找所有材料中最好的性能时，这些材料中的许多都是金属氧化物，需要从分子水平上理解这些性能。金属氧化物作为一个分子的合成看似简单，但对化学家来说却是一个长期的挑战，未知的世界正在哀号。在这项研究中，我们发现了无机络合物中的氧离子与金属原子配位的化学，并证明了配位化学可以扩展到纯无机氧化物化学的世界。无机络合物是由多氧钒酸与作为Lewis酸的金属阳离子结合而成的。在乙腈溶液中，金属源的Lewis酸性促进了偏钒酸物种的缩合反应，即三聚或四聚。在非水溶液中合成了An、Ni(II)、Cu(II)、Zn(II)的纯有机络合物，并合成了各种含冠型氧阴离子配体的氧化物分子。这项研究中最有趣的发现是手性无机分子的发现。当我们在硝酸盐模板存在下缩合钒酸盐时，我们发现通过硝酸盐模板形成了两个十八碳钒酸链，链的两端被V05锥体单元覆盖。另一种观点认为，第一个双螺旋无机分子已经出现。钒的基础氧化物的新化学具有重要的战略意义，从分子化学的角度来理解氧化物中各种性质的变化。本研究探索了氧化物分子的化学组成，实现了许多有趣的盘状、笼状、手性氧化物分子的形成，为功能材料的进一步研究奠定了基础。

Metal oxide is one of a popular material in high-tech world in modern society such as superconductivities, magnetic or semiconductor properties, and catalysts. When we look for the best properties of all, many of these materials are turning up to be metal oxides, and need to understand those properties from the molecular level. The synthesis of metal oxide as a molecule is seemingly easy, but is a challenge for a chemist for a long time, and unexplored world is wailing. In this study, we discover the chemistry of inorganic complex in which the oxide anion is coordinated to the metal atoms, and we proved the coordination chemistry can be expanded to the world of pure inorganic oxide chemistry. The inorganic complex was achieved by the combination of polyoxovanadates and the metal cations as Lewis acid The Lewis acidity of the metal sources prompt the condensation reaction of the metavanadate species, which is tri or tetramer in acetonitrile solution. The resulting pureinorganic complex of an, Ni(II), Cu(II), and Zn(II) have been synthesized in non-aqueous solution and various oxide molecule with crown-type oxide anion ligands were synthesized. Most of the interesting finding in this study is a discovery of the chiral inorganic molecule. When we condense the vanadate under the presence of nitrate template, we found the formation of two octadecavanadate chains through the nitrate template capped the both ends of the chain by V05 pyramidal units. In other view, the first double helical inorganic molecule had been emerged.The new chemistry of fundamental oxide of vanadium is strategic importance, and the understanding of the variety of properties in oxide can be tackled from the point of molecular chemistry. This study explorer the chemistry of oxide molecule and many interesting formation of disk, cage, chiral oxide molecule have been realized, and further studies will provide the extention toward the functional materials.