Jiang Haoyu, Čavlović Daniel, Jiang Qifeng, Ng Fay, Bao Si Tong, Telford Evan J, Steigerwald Michael L, Roy Xavier, Nuckolls Colin, McNeill Jeffrey M
Department of Chemistry, Columbia University, New York, New York 10027, United States.
J Am Chem Soc. 2025 Apr 16;147(15):12982-12988. doi: 10.1021/jacs.5c02723. Epub 2025 Apr 3.
Creating new chiral molecular and macromolecular systems that can polarize the spin of electrons has the dual promise of both applications in spintronics and a fundamental understanding of their origins. Here, we put forward two optically active helical ladder dimers from perylene diimide-based twistacenes and helicenes. We detail a scalable method to separate the helices for each of these systems and methods to functionalize them with thiol groups that allow for self-assembled monolayer formation on metal surfaces. We probed these monolayers with conductive atomic force microscopy, revealing that they are highly conductive. If the substrate is magnetized, then the current we measure with conductive atomic force microscopy is controlled by the handedness of the helices used to form the monolayers. Furthermore, helices of the same handedness for either the twistacene or helicene (right-handed helices vs left-handed helices) produce high (or low) currents in devices with the same magnetization. Importantly, we find a correlation between the magnetic field dependence of the conductivity and the helicity of the molecules, suggesting a link between these two properties, independent of the sign of their electronic circular dichroism.
创建能够使电子自旋极化的新型手性分子和大分子体系,有望在自旋电子学中得到应用,并对其起源有基本的认识。在此,我们提出了两种基于苝二亚胺并四苯和螺旋烯的旋光性螺旋梯形二聚体。我们详细介绍了一种可扩展的方法,用于分离这些体系中的螺旋结构,以及用硫醇基团对其进行功能化的方法,这些硫醇基团可用于在金属表面形成自组装单分子层。我们用导电原子力显微镜对这些单分子层进行了探测,发现它们具有高导电性。如果衬底被磁化,那么我们用导电原子力显微镜测量的电流就由用于形成单分子层的螺旋结构的手性所控制。此外,对于并四苯或螺旋烯,相同手性的螺旋结构(右旋螺旋与左旋螺旋)在具有相同磁化的器件中会产生高(或低)电流。重要的是,我们发现电导率的磁场依赖性与分子的螺旋度之间存在相关性,这表明这两种性质之间存在联系,而与它们的电子圆二色性的符号无关。