J Org Chem. 2014 Feb 7;79(3):1184-91. doi: 10.1021/jo4026176.
A practical method for the preparation of novel tripodal tris(porphyrinato-urea) TP3 1 was readily achieved. Because of its appreciable preorganized triangular cone-shaped cavity resulting from the intramolecular hydrogen bonds of the tripodal tris-urea backbone, this porphyrin trimer host was found to have a high affinity toward fullerenes to form stable inclusion complexes in solution. A 120-fold binding selectivity toward C70 (Kassoc = 1.81 × 10(7) M(–1)) over C60 (Kassoc = 1.51 × 10(5) M(–1)) was further achieved in toluene. Moreover, the dissociation of such inclusion complexes can be easily realized by introducing H2PO4(–), and recapturing of the fullerene can be achieved after withdrawing H2PO4(–) by Ca(2+). A recyclable process for the inclusion and release of fullerene was therefore built by alternately feeding H2PO4(–) and Ca(2+). Benefiting from this approach, TP3 1 was sequentially applied to isolate C70 from the C60-enriched fullerene mixture successfully.
一种新型三脚架三（卟啉脲）TP3 1 的实用制备方法得以顺利实现。由于三脚架三脲骨架的分子内氢键导致其具有可观的预组织的三角锥形空腔，因此该卟啉三聚体主体对富勒烯具有高亲和力，能够在溶液中形成稳定的包合复合物。在甲苯中，相对于 C60（Kassoc = 1.51 × 10(5) M(–1)），对 C70 的结合选择性进一步达到 120 倍（Kassoc = 1.81 × 10(7) M(–1)）。此外，通过引入 H2PO4(–) 可以很容易地实现这种包合复合物的解离，并且在除去 H2PO4(–) 后可以通过 Ca(2+) 来捕获富勒烯。因此，通过交替进料 H2PO4(–) 和 Ca(2+)，构建了富勒烯的包合和释放的可回收过程。得益于这种方法，TP3 1 被顺序应用于成功地从 C60 富勒烯混合物中分离 C70。
