A molybdenum crown cluster forms discrete inorganic-organic nanocomposites with metalloporphyrins.
A molybdenum crown cluster forms discrete inorganic-organic nanocomposites with metalloporphyrins.
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DOI：
10.1002/anie.200460990
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发表时间：
2004-11
影响因子：
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通讯作者：
Akihiko Tsuda;Eri Hirahara;Yeong‐Sang Kim;Hiroyuki Tanaka;T. Kawai;T. Aida
中科院分区：
文献类型：
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作者：
Akihiko Tsuda;Eri Hirahara;Yeong‐Sang Kim;Hiroyuki Tanaka;T. Kawai;T. Aida
钼蓝(MB)是由MoVI在酸性水溶液中部分还原而形成的一种鲜艳的蓝色无机材料。它是由混价MoV和MoVI中心组成的多钼酸(POM)团簇的混合物。[1-3]虽然最初的探索是在200多年前进行的，[4]POM团簇的结构分析第一次成功的报道是在1995年，当时Müler和他的同事分离了一个冠状POM团簇并获得了它的晶体结构。[5]到目前为止，他们还成功地确定了具有中空和球形形状的大型POM团簇的结构。[6，7]尽管POM团簇在材料科学中具有有趣的潜力，目前还没有利用这种无机纳米物体来制备离散的无机/有机纳米复合材料的报道。在这里，我们报道了冠状POM(钼冠簇；MC)，当与具有中位氨基苯基取代的金属卟啉混合时，形成离散的包合物，其中MC的无机腔可以容纳多达三个客体化合物分子，从而得到空间隔离的金属卟啉分子(方案1)。
Molybdenum blue (MB), formed by partial reduction of MoVI in an acidic aqueous solution, is a striking inorganic material due to its vivid blue color. It is a mixture of polyoxomolybdate (POM) clusters consisting of mixed-valent MoV and MoVI centers.[1–3] Although the initial exploration was made more than 200 years ago,[4] the first success in structural analysis of POM clusters was only reported in 1995, when Müller and coworkers isolated a crown-shaped POM cluster and obtained its crystal structure.[5] To date, they have also succeeded in structural determination of large POM clusters with hollow and spherical shapes.[6, 7] Despite their interesting potentials in materials sciences, no examples have yet been reported of the utilization of such inorganic nano-objects for the fabrication of discrete inorganic/organic nanocomposite materials. Herein we report that the crown-shaped POM (molybdenum crown cluster; MC), upon mixing with metalloporphyrins having meso-aminophenyl substituents, forms discrete inclusion complexes, where the inorganic cavity of MC can accommodate up to three molecules of the guest compounds, to give spatially isolated metalloporphyrin molecules (Scheme 1).