Center of Micro- and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen , Adolf-Reichwein-Strasse-2, 57068 Siegen, Germany.
J Org Chem. 2017 Jan 6;82(1):343-352. doi: 10.1021/acs.joc.6b02436. Epub 2016 Dec 27.
In our quest to develop artificial multistate devices, we synthesized the nanomechanical switch 1 that is characterized by a tetrahedral core equipped with four pending arms. The rotary arm with its azaterpyridine terminal is intramolecularly coordinated to a zinc(II) porphyrin station that is the terminus of another arm in 1. The two other arms carry identical sterically shielded phenanthroline stations. The 2-fold alternate addition of a copper(I) ion and [1,10]-phenanthroline (1 equiv each) results in the formation of five different switching states (State I→ State II→ State III→ State IV→ State V → State I), which force the toggling arm to move back and forth between the zinc(II) porphyrin and phenanthroline stations separated by a distance of 25 Å. All switching states constitute clean single species, except for State III, and thus are fully characterized by spectroscopic methods and elemental analysis. Finally, the initial state of nanoswitch was reset by addition of cyclam for complete removal of the copper(I) ions.
在我们开发人工多稳态器件的探索中，我们合成了纳米机械开关 1，其特征是具有四面体核心的四个悬垂臂。带有吖啶吡啶末端的旋转臂在分子内与锌（II）卟啉站配位，该站是 1 中另一个臂的末端。另外两个臂携带相同的空间位阻菲咯啉站。铜（I）离子和[1,10]-菲咯啉（各 1 当量）的 2 倍交替加成导致形成五个不同的开关状态（状态 I→状态 II→状态 III→状态 IV→状态 V →状态 I），这迫使拨动臂在锌（II）卟啉和菲咯啉站之间来回移动，距离为 25 Å。除了状态 III 之外，所有的开关状态都构成了干净的单一物种，因此都可以通过光谱方法和元素分析进行充分表征。最后，通过添加环戊二胺来完全去除铜（I）离子，将纳米开关的初始状态重置。
