Center for Micro- and Nanochemistry and Engineering, Organische Chemie I, Adolf-Reichwein Strasse, Universität Siegen, D-57068 Siegen, Germany.
J Org Chem. 2011 Sep 16;76(18):7466-73. doi: 10.1021/jo201252q. Epub 2011 Aug 24.
The heteroleptic supramolecular double-decker porphyrin 1 was synthesized with DABCO as a guest between two cofacial porphyrin units as characterized by (1)H NMR and ESI-MS. While DABCO is not seen to tumble inside the cavity, even at higher temperatures (80 °C), such motion was triggered upon addition of various coordinating ligands (quinuclidine, 4-bromopyridine, or excess of DABCO). Different stoichiometric amounts were needed depending on the n donor quality of the added ligands to initiate tumbling of the "inside" DABCO. As demonstrated in an example with excess DABCO, the tumbling was stopped by lowering the temperature to -50 °C.
具有 DABCO 作为两个共面卟啉单元之间客体的杂化超分子双层卟啉 1 通过 1H NMR 和 ESI-MS 进行了表征。虽然 DABCO 没有在腔内翻转，即使在较高温度（80°C）下也是如此，但在加入各种配位配体（奎宁环、4-溴吡啶或过量的 DABCO）时，这种运动被触发。根据添加配体的 n 供体质量的不同，需要不同的化学计量比来引发“内部”DABCO 的翻转。如过量 DABCO 的实例所示，通过将温度降低至-50°C 可以停止翻转。
