Chichak Kelly S, Cantrill Stuart J, Pease Anthony R, Chiu Sheng-Hsien, Cave Gareth W V, Atwood Jerry L, Stoddart J Fraser
Department of Chemistry and Biochemistry and the California NanoSystems Institute, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095, USA.
Science. 2004 May 28;304(5675):1308-12. doi: 10.1126/science.1096914.
The realization of the Borromean link in a wholly synthetic molecular form is reported. The self-assembly of this link, which is topologically achiral, from 18 components by the template-directed formation of 12 imine and 30 dative bonds, associated with the coordination of three interlocked macrocycles, each tetranucleating and decadentate overall, to a total of six zinc(II) ions, is near quantitative. Three macrocycles present diagonally in pairs, six exo-bidentate bipyridyl and six endo-diiminopyridyl ligands to the six zinc(II) ions. The use, in concert, of coordination, supramolecular, and dynamic covalent chemistry allowed the highly efficient construction, by multiple cooperative self-assembly processes, of a nanoscale dodecacation with an approximate diameter of 2.5 nanometers and an inner chamber of volume 250 A(3), lined with 12 oxygen atoms.
报道了完全以合成分子形式实现的博罗梅安环。这种拓扑非手性的环通过模板导向形成12个亚胺键和30个配位键,由18个组分自组装而成,这与三个互锁大环(每个大环整体为四核且十齿)与总共六个锌(II)离子的配位相关,产率接近定量。三个大环成对呈对角线排列,向六个锌(II)离子提供六个外双齿联吡啶和六个内二亚氨基吡啶配体。协同使用配位化学、超分子化学和动态共价化学,通过多个协同自组装过程,高效构建了一个纳米级十二价阳离子,其直径约为2.5纳米,内腔体积为250 ų,内衬12个氧原子。