Wang Yuping, Frasconi Marco, Stoddart J Fraser
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova 35131, Italy.
ACS Cent Sci. 2017 Sep 27;3(9):927-935. doi: 10.1021/acscentsci.7b00219. Epub 2017 Aug 14.
Ever since their discovery, stable organic radicals have received considerable attention from chemists because of their unique optical, electronic, and magnetic properties. Currently, one of the most appealing challenges for the chemical community is to develop sophisticated artificial molecular machines that can do work by consuming external energy, after the manner of motor proteins. In this context, radical-pairing interactions are important in addressing the challenge: they not only provide supramolecular assistance in the synthesis of molecular machines but also open the door to developing multifunctional systems relying on the various properties of the radical species. In this Outlook, by taking the radical cationic state of 1,1'-dialkyl-4,4'-bipyridinium (BIPY) as an example, we highlight our research on the art and science of introducing radical-pairing interactions into functional systems, from prototypical molecular switches to complex molecular machines, followed by a discussion of the (i) limitations of the current systems and (ii) future research directions for designing BIPY-based molecular machines with useful functions.
自从被发现以来,稳定的有机自由基因其独特的光学、电子和磁性特性而受到化学家们的广泛关注。目前,化学界最具吸引力的挑战之一是开发出复杂的人工分子机器,这些机器能够像运动蛋白一样通过消耗外部能量来做功。在这种背景下,自由基对相互作用对于应对这一挑战至关重要:它们不仅在分子机器的合成中提供超分子辅助,还为开发依赖自由基物种各种特性的多功能系统打开了大门。在本展望中,以1,1'-二烷基-4,4'-联吡啶鎓(BIPY)的自由基阳离子态为例,我们重点介绍了我们在将自由基对相互作用引入功能系统的艺术与科学方面的研究,从典型的分子开关到复杂的分子机器,随后讨论了(i)当前系统的局限性以及(ii)设计具有有用功能的基于BIPY的分子机器的未来研究方向。