Naghibi Saman, Sangtarash Sara, Kumar Varshini J, Wu Jian-Zhong, Judd Martyna M, Qiao Xiaohang, Gorenskaia Elena, Higgins Simon J, Cox Nicholas, Nichols Richard J, Sadeghi Hatef, Low Paul J, Vezzoli Andrea
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
School of Engineering, University of Warwick, Coventry, CV4 7AL, UK.
Angew Chem Int Ed Engl. 2022 Jun 7;61(23):e202116985. doi: 10.1002/anie.202116985. Epub 2022 Apr 5.
Integrating radical (open-shell) species into non-cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open-shell character is generally lost in contact with the metallic electrodes. Herein, single-molecule devices incorporating a 6-oxo-verdazyl persistent radical have been fabricated using break-junction techniques. The open-shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed-shell anionic state in a single-molecule transistor configuration. Furthermore, electronically driven rectification arises from bias-dependent alignment of the open-shell resonances. The integration of radical character, transistor-like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open-shell species.
将自由基（开壳层）物种集成到非低温纳米器件中是释放分子电子学潜力的关键。尽管已经在这个问题上投入了很多努力，但在没有化学/电化学势的情况下，开壳层特性在与金属电极接触时通常会丧失。在此，利用断接技术制备了包含6-氧代-连氮自由基的单分子器件。开壳层特性在室温下得以保留，并且电化学门控允许在单分子晶体管配置中原位还原为闭壳层阴离子状态。此外，电子驱动的整流源于开壳层共振的偏压依赖性排列。在单个分子组件中集成自由基特性、类似晶体管的开关和整流为进一步研究开壳层物种的电子、磁和热电性质铺平了道路。
