Zhang Min, De Bo Guillaume
School of Chemistry , University of Manchester , Oxford Road , Manchester M13 9PL , United Kingdom.
J Am Chem Soc. 2018 Oct 10;140(40):12724-12727. doi: 10.1021/jacs.8b08590. Epub 2018 Sep 26.
Mechanical bonds are known to efficiently absorb mechanical energy at low forces, but their behavior at high forces is unknown. Here we investigate the impact of a mechanical bond on the rate of activation of a Diels-Alder mechanophore. Using a combination of experimental and computational techniques, we found that the rate of a retro-Diels-Alder reaction under tension is decreased when the mechanophore is embedded in the axle of a rotaxane due to the presence of a competing high-stress region at the junction between the macrocycle and the axle.
已知机械键能在低力作用下有效吸收机械能，但其在高力作用下的行为尚不清楚。在此，我们研究了机械键对狄尔斯-阿尔德机械发色团活化速率的影响。通过结合实验和计算技术，我们发现，当机械发色团嵌入轮烷的轴中时，由于大环与轴之间的连接处存在竞争高应力区域，张力作用下的逆狄尔斯-阿尔德反应速率会降低。
