para-Octaiodophenylsilsesquioxane, [p-IC6H4SiO(1.5)]8, a nearly perfect nano-building block.
para-Octaiodophenylsilsesquioxane, [p-IC6H4SiO(1.5)]8, a nearly perfect nano-building block.
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DOI：
10.1021/nn700196d
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发表时间：
2008-01
期刊：
影响因子：
17.1
通讯作者：
M. Roll;M. Asuncion;J. Kampf;R. Laine
中科院分区：
文献类型：
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作者：
M. Roll;M. Asuncion;J. Kampf;R. Laine
八官能八苯基倍半硅氧烷[ROPS，（RC 6 H4 SiO（1.5））8]的立方对称性加上1 nm的直径提供了特殊的潜力，组装材料的三维与完美的控制周期性和潜在的定制全球性能在纳米长度尺度。OPS本身是非常惰性和不溶性的，只能通过亲电反应进行官能化，这很困难，取代选择性也很差。然而，功能化的OPS产品是稳健的和高度可溶的，提供容易的纯化和加工。与以前的研究相反，我们在此报道OPS与ICl在低于环境温度下反应，以良好的产率和优异的选择性提供（在重结晶之后）[p-IC 6 H4 SiO（1.5）]8或I8 OPS：如通过Si-C键的H2 O2/F-裂解产生碘苯酚所确定的，> 99%的单碘代取代和>93%的帕拉取代。I8 OPS又可使用常规催化偶联反应官能化以提供多组>93%对位取代的官能化化合物（炔、烯烃、芳基胺、膦酸酯、芳基胺、多芳族化合物等），这表明有可能开发多种纳米构建块来组装各种材料，其中一些具有新颖的光子、电子和结构特性。
The cubic symmetry of octafunctional octaphenylsilsesquioxanes [ROPS, (RC6H4SiO(1.5))8] coupled with a 1 nm diameter offers exceptional potential to assemble materials in three dimensions with perfect control of periodicity and the potential to tailor global properties at nanometer length scales. OPS itself is very inert and insoluble and can only be functionalized via electrophilic reactions with difficulty and with poor substitutional selectivity. However, functionalized OPS products are robust and highly soluble, offering easy purification and processing. In contrast to previous studies, we report here that OPS reacts with ICl at sub-ambient temperatures to provide (following recrystallization) [p-IC6H4SiO(1.5)]8, or I8OPS, in good yields and with excellent selectivity: >99% mono-iodo substitution with >93% para substitution as determined by H2O2/F- cleavage of the Si-C bonds to produce iodophenols. I8OPS in turn can be functionalized using conventional catalytic coupling reactions to provide sets of >93% para-substituted, functionalized compounds (alkynes, alkenes, aryl amines, phosphonates, aryl amines, polyaromatics, etc.), suggesting the potential to develop diverse nano-building blocks for the assembly of a wide variety of materials, some with novel photonic, electronic, and structural properties.