Triptycene‐Derived Calix[6]arenes: Synthesis,Structures, and Their Complexation with Fullerenes C60 and C70 |
| |
Authors: | Xiao‐Hong Tian Chuan‐Feng Chen Prof |
| |
Institution: | 1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China), Fax: (+86)?10‐62554449;2. Graduate School, Chinese Academy of Sciences, Beijing 100049 (China) |
| |
Abstract: | Two pairs of novel triptycene‐derived calix6]arenes 4 a , b and 5 a , b have been efficiently synthesized through both one‐pot and two‐step fragment‐coupling strategies starting from 2,7‐bis(hydroxymethyl)‐1,8‐dimethoxytriptycene 1 . Subsequent demethylation of 4 a , b and 5 a , b with BBr3 in dry dichloromethane gave the macrocyclic compounds 6 a , b and 7 a , b . Treatment of either 4 a or 6 a with AlCl3 resulted in the same debutylated product 8 , while 9 was similarly obtained from either 5 a or 7 a . Structural studies revealed that all of the macrocycles have well‐defined structures with fixed conformations both in solution and in the solid state owing to the introduction of the triptycene moiety with a rigid three‐dimensional (3D) structure, making them very different from their classical calix6]arene counterparts. As a consequence, it was found that all of these the triptycene‐derived calix6]arenes could encapsulate small neutral molecules in their cavities in the solid state. Moreover, it was also found that the macrocycles 4 b and 5 b showed highly efficient complexation abilities toward fullerenes C60 and C70, forming 1:1 complexes with association constants ranging from (5.22±0.20)×104 to (8.68±0.30)×104 M ?1. |
| |
Keywords: | calixarenes fullerenes host– guest systems synthesis design triptycene |
|
|