Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, 211800, P.R. China).
Angew Chem Int Ed Engl. 2016 Jul 4;55(28):7958-62. doi: 10.1002/anie.201602135. Epub 2016 Apr 20.
Pseudo-octahedral M(II) 6 L4 capsules result from the subcomponent self-assembly of 2-formylphenanthroline, threefold-symmetric triamines, and octahedral metal ions. Whereas neutral tetrahedral guests and most of the anions investigated were observed to bind within the central cavity, tetraphenylborate anions bound on the outside, with one phenyl ring pointing into the cavity. This binding configuration is promoted by the complementary arrangement of the phenyl rings of the intercalated guest between the phenanthroline units of the host. The peripherally bound, rapidly exchanging tetraphenylborate anions were found to template an otherwise inaccessible capsular structure in a manner usually associated with slow-exchanging, centrally bound agents. Once formed, this cage was able to bind guests in its central cavity.
假八面体 M(II)6L4 胶囊是由亚组分自组装 2-甲酰基菲咯啉、三倍对称三胺和八面体金属离子形成的。在研究过程中发现，中性四面体形客体和大多数阴离子被观察到结合在中央腔体内，而四苯硼酸阴离子则结合在外部，其中一个苯环指向腔体内。这种结合构型是由客体插入的苯环与主体中菲咯啉单元之间的互补排列促进的。在这种情况下，外围结合的、快速交换的四苯硼酸阴离子模板化了一种原本无法进入的胶囊结构，这种方式通常与缓慢交换的、中央结合的试剂有关。一旦形成，这种笼状结构就能够在其中央腔体内结合客体。
