Li Chifeng, Mizuno Noritaka, Yamaguchi Kazuya, Suzuki Kosuke
Department of Applied Chemistry, School of Engineering , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku, Tokyo 113-8656 , Japan.
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST) , 4-1-8 Honcho , Kawaguchi , Saitama 332-0012 , Japan.
J Am Chem Soc. 2019 May 15;141(19):7687-7692. doi: 10.1021/jacs.9b02541. Epub 2019 Apr 23.
The development of novel systems for metal-organic architectures is an attractive research field because they are fascinating materials with unexplored functions. Lacunary polyoxometalates (POMs) offer structurally well-defined coordination sites with various coordination directions and numbers in addition to the designable properties; thus, lacunary POMs are ideal building blocks for inorganic-organic architectures. However, their utilization is currently limited by their low stability and difficulty in controlling the reactivity. Here, we report the successful self-assembly of anionic POM-organic architectures comprising multivacant lacunary POMs and pyridyl ligands. By introducing pyridine moieties to its vacant sites, the trivacant lacunary phosphomolybdate [A-α-PMoO] is significantly stabilized in organic solvents. Furthermore, the resultant structure can be utilized as a stable and reactive building block to synthesize a dimer pillared by 4,4'-bipyridyl and a tetramer bridged by two cofacial porphyrin ligands, which can intercalate aromatic molecules.
新型金属有机结构体系的开发是一个具有吸引力的研究领域，因为它们是具有未被探索功能的迷人材料。缺位多金属氧酸盐（POMs）除了具有可设计的性质外，还提供结构明确的配位位点，具有各种配位方向和数量；因此，缺位POMs是无机-有机结构的理想构建块。然而，它们目前的应用受到其低稳定性和控制反应性困难的限制。在这里，我们报告了由多空位缺位POMs和吡啶基配体组成的阴离子POM-有机结构的成功自组装。通过将吡啶部分引入其空位，三空位缺位磷钼酸盐[A-α-PMoO]在有机溶剂中得到显著稳定。此外，所得结构可以用作稳定且具有反应活性的构建块，以合成由4,4'-联吡啶支撑的二聚体和由两个共面卟啉配体桥接的四聚体，后者可以嵌入芳香分子。
