Crowley James D, Leigh David A, Lusby Paul J, McBurney Roy T, Perret-Aebi Laure-Emmanuelle, Petzold Christiane, Slawin Alexandra M Z, Symes Mark D
School of Chemistry, University of Edinburgh, The King's Buildings, West Mains Road, Edinburgh EH9 3JJ, United Kingdom.
J Am Chem Soc. 2007 Dec 5;129(48):15085-90. doi: 10.1021/ja076570h. Epub 2007 Nov 9.
We report the design, synthesis, characterization, and operation of a [2]rotaxane in which a palladium-complexed macrocycle can be translocated between 4-dimethylaminopyridine and pyridine monodentate ligand sites via reversible protonation, the metal remaining coordinated to the macrocycle throughout. The substitution pattern of the ligands and the kinetic stability of the Pd-N bond means that changing the chemical state of the thread does not automatically cause a change in the macrocycle's position in the absence of an additional input (heat and/or coordinating solvent/anion). Accordingly, under ambient conditions any of the four sets of protonated and neutral, stable, and metastable co-conformers of the [2]rotaxane can be selected, manipulated, isolated, and characterized.
我们报告了一种[2]轮烷的设计、合成、表征及操作，其中与钯络合的大环可通过可逆质子化在4-二甲基氨基吡啶和吡啶单齿配体位点之间移位，在此过程中金属始终与大环保持配位。配体的取代模式以及Pd-N键的动力学稳定性意味着，在没有额外输入（加热和/或配位溶剂/阴离子）的情况下，改变链的化学状态不会自动导致大环位置的改变。因此，在环境条件下，可以选择、操控、分离和表征[2]轮烷的四组质子化与中性、稳定和亚稳共构象中的任何一种。
