Identifying the Conformational Isomers of Single-Molecule Cyclohexane at Room Temperature

构象异构是化学中的基本问题。然而对于环己烷等柔性分子，由于其在室温下极快的互变异构过程，基于系综的表征方法（如核磁等）只能得到所有构象平均贡献的结果。为了应对这一挑战，化学化工学院洪文晶教授与夏海平教授课题组为在室温条件下对柔性分子构象的定量分析与表征这一挑战，课题组成功实现了在室温条件下对环己烷两种椅式构象的电学表征与比例识别。同时，通过纳米电极间隙对分子的限域作用，发现在宏观尺度下极不稳定的扭船式中间体得以在单分子尺度稳定存在，这为不稳定中间体的研究提供了重要表征方法。 这一研究工作是在化学化工学院洪文晶教授、夏海平教授共同指导下完成的，iChEM直博生唐淳与化工系研究生唐永翔为论文共同第一作者。师佳副教授与刘俊扬副研究员为该工作提供了指导，博士后陈志昕、博士研究生陈李珏以及研究生叶艺玲、严哲玮、张珑漪共同参与了该工作。【Abstract】Isomerism reflects the ubiquitous nature that molecules with the same molecular formula show different structures. The interconversion between conformational isomers of flexible molecules is quite fast owing to the low barriers of around 10 kcal mol−1, leading to average signal contributed by all the possible isomers characterized by ensemble methods. On this account, identifying the conformational isomers of flexible molecules at room temperature has a substantial challenge. Here, we develop a single-molecule approach to identify the conformational isomers of cyclohexane at room temperature through the single-molecule electrical characterization. By noise analysis and feature extraction of the conductance of single-molecule junctions, we quantificationally identified two chair isomers of cyclohexane at room temperature, while such identification is only feasible at low temperatures by ensemble characterization. The strategy to apply the single-molecule approach to identify conformational isomers paves the avenue to investigate the isomerization of flexible molecules beyond the ensemble methods.This work was supported by the National Natural Science Foundation of China (nos, 21722305, 21673195, 21703188, and U1705254), the National Key R&D Program of China (2017YFA0204902), China Postdoctoral Science Foundation (no. 2017M622060), and the Fundamental Research Funds for Xiamen University (20720190002).该工作获得了科技部国家重点研发计划、国家自然科学基金等项目的资助，也得到了固体表面物理化学国家重点实验室、能源材料化学协同创新中心的支持

Room-temperature quantum interference in single perovskite quantum dot junctions

钙钛矿材料由于其高量子产率、载流子迁移率和独特的光致发光特性而在光电材料领域存在诸多潜在的重要应用。研究钙钛矿材料在纳米尺度下电荷输运的独特尺寸效应对钙钛矿光电器件的设计和开发具有重要的指导意义。洪文晶教授课题组基于机械可控裂结技术自主研发了具有皮米级位移调控灵敏度和飞安级电学测量精度的精密科学仪器，对南开大学李跃龙副教授团队合成的钙钛矿量子点进行了深入表征，研究工作成功将量子干涉的研究体系拓展至在光电领域具有重要应用的钙钛矿材料领域，为未来制备基于量子干涉效应的新型钙钛矿器件提供了一种全新的思路。 这一跨学科国际合作研究工作是在化学化工学院洪文晶教授、英国Lancaster 大学物理系Colin J. Lambert教授以及南开大学电子信息与光电工程学院李跃龙副教授的共同指导下完成的。化工系硕士研究生郑海宁、Lancaster University大学Songjun Hou博士、南开大学硕士研究生辛晨光为论文第一作者。博士后林禄春，博士研究生谭志冰、郑珏婷，硕士研究生蒋枫、张珑漪，本科生何文翔、李庆民等参与了论文的研究工作。刘俊扬特任副研究员、师佳副教授和萨本栋微纳米研究院杨扬副教授也参与了部分指导工作。The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of roomtemperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Auhalogen coupling. We also observe a distinct conductance ‘jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ‘jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials.This work was supported by the National Key R&D Program of China (2017YFA0204902, 2014DFE60170, 2018YFB1500105), the National Natural Science Foundation of China (Nos. 21673195, 21503179, 21490573, 61674084, 61874167), the Open Fund of the Key Laboratory of Optical Information Science & Technology (Nankai University) of China, the Fundamental Research Funds for the Central Universities of China (63181321, 63191414, 96173224), and the 111 Project (B16027), the Tianjin Natural Science Foundation (17JCYBJC41400), FET Open project 767187—QuIET, the EU project BAC-TO-FUEL and the UK EPSRC projects EP/N017188/1, EP/M014452/1. 该工作得到国家重点研发计划课题（2017YFA0204902）、国家自然科学基金（21673195、21503179、21490573）、厦门大学“人工智能分析引擎”双一流重大专项等项目的资助，也得到了固体表面物理化学国家重点实验室、能源材料化学协同创新中心的支持