Abstract:
Structural variants of high-nuclearity clusters are extremely important for their modular assembly study and functional expansion, yet the synthesis of such giant structural variants remains a great challenge. Herein, we prepared a lantern-type giant polymolybdate cluster (L-Mo132 ) containing equal metal nuclearity with the famous Keplerate type Mo132 (K-Mo132 ). The skeleton of L-Mo132 features a rare truncated rhombic triacontrahedron, which is totally different with the truncated icosahedral K-Mo132 . To the best of our knowledge, this is the first time to observe such structural variants in high-nuclearity cluster built up of more than 100 metal atoms. Scanning transmission electron microscopy reveals that L-Mo132 has good stability. More importantly, because the pentagonal [Mo6 O27 ]n- building blocks in L-Mo132 are concave instead of convex in the outer face, it contains multiple terminal coordinated water molecules on its outer surface, which make it expose more active metal sites to display superior phenol oxidation performance, which is more higher than that of K-Mo132 coordinated in M=O bonds on the outer surface.
摘要:
高核团的结构变体对于其模块化组装研究和功能扩展极为重要,然而,这种巨大的结构变体的合成仍然是一个巨大的挑战。在这里,我们准备了一个灯笼型巨型多钼酸盐簇(L-Mo132),其金属核与著名的Keplerate型Mo132(K-Mo132)相等。L-Mo132的骨架具有罕见的截头菱形三面体,这与截短的二十面体K-Mo132完全不同。据我们所知,这是首次在由100多个金属原子组成的高核团簇中观察到这种结构变体。扫描透射电子显微镜显示L-Mo132具有良好的稳定性。更重要的是,因为L-Mo132中的五边形[Mo6O27]n-构建块在外表面是凹的而不是凸的,它的外表面含有多个末端配位的水分子,这使得它暴露更多的活性金属位点,以显示优越的苯酚氧化性能,其比K-Mo132在外表面上的M=O键配位的更高。