Murphy Paul, Dalgarno Scott J, Paterson Martin J
Institute of Chemical Sciences, Heriot Watt University , Edinburgh EH14 4AS, United Kingdom.
J Phys Chem A. 2017 Oct 19;121(41):7986-7992. doi: 10.1021/acs.jpca.7b07297. Epub 2017 Oct 5.
The efficacy of calixarenes for the storage and/or detection of small guest molecules at the upper-rim is well-known. As part of our continuing efforts to investigate the ability to fine-tune the structure and hence host-guest binding characteristics of calixarenes, we present a systematic investigation of the effect of methylation of the lower-rim tetraphenolic pocket of calix[4]arene (C[4]) on binding at the upper-rim for a test-suite of guest molecules consisting of H, O, N, HO, CO, NH, HS, NO, HCN, and SO. Results of the effects on the host-guest binding for all permutations of single, double, triple and quadruple methylations are presented. It was found that while a tetraphenolic C[4] host does not discriminate between many of the guest molecules in terms of binding energies, progressively methylated lower-rim C[4] hosts introduce differences in guest binding energies within the upper cavity to the extent where it may be possible to competitively bind one guest over another over a wide range of guests. In this regard, this family of methylated C[4] hosts show promise as gas separation devices.
杯芳烃在上缘储存和/或检测小分子客体分子的功效是众所周知的。作为我们持续研究微调杯芳烃结构从而调控主客体结合特性能力的一部分，我们对杯[4]芳烃（C[4]）下缘四酚口袋甲基化对一系列由H、O、N、HO、CO、NH、HS、NO、HCN和SO组成的客体分子在上缘结合的影响进行了系统研究。给出了单甲基化、双甲基化、三甲基化和四甲基化所有排列对主客体结合影响的结果。结果发现，虽然四酚C[4]主体在结合能方面对许多客体分子没有区分能力，但下缘逐步甲基化的C[4]主体会在上腔引入客体结合能的差异，以至于在广泛的客体范围内有可能竞争性地结合一种客体而非另一种。在这方面，这类甲基化C[4]主体有望成为气体分离装置。
