Entrapment, Manipulation and Reactions of Molecules at the Nanoscale

该项目解决了与控制纳米尺度分子的位置、方向和动能相关的科学最基本的挑战之一。该项目将开发将分子限制在一维（纳米管）和二维（石墨烯）纳米材料中的创新方法，以研究其行为并利用其功能特性。单壁碳纳米管（内径1-2 nm）是世界上最小的试管，可以有效地将分子捕获在自由度非常有限的圆柱形空腔中。例如，在先前的研究中用作模型分子的富勒烯已经清楚地证明了分子的位置、取向、平移和旋转运动--所有这些都受到主体纳米管的显著影响[Acc. Chem. Res.，2005，38，901]。在这个项目中，我们将扩展这一概念，并引入分子行为的主动控制，使用纳米管作为电子或声子的纳米管道，或纳米天线收集电磁辐射并将能量转移到捕获的分子。其中一个目标是触发和控制分子的反应，并在单分子水平上引导它们转化为所需的产物[ACS Nano，2017，in press，http://pubs.acs.org/doi/abs/10.1021/acsnano.6b08228]，这可能会彻底改变我们研究化学反应和制造材料的方式。该项目中为纳米管开发的方法将转移到石墨烯单层或石墨烯双层内的分子，其中纳米管中的一维限制原理将在二维中扩展和探索。特别地，导致一维链状或带状产物的分子间反应[Nature Mater.，2011，10，687]将用于石墨烯上的分子以构建具有定制结构和组成以及可调电子和光学性质的共价有机框架（COF）材料，从而解决石墨烯技术的最关键挑战之一。

This project addresses one of the most fundamental challenges of science related to control of positions, orientations and kinetic energy of molecules at the nanoscale. Innovative methodologies for confinement of molecules in 1D (nanotube) and 2D (graphene) nanomaterials will be developed in this project in order to study their behaviour and to harness their functional properties.Single-walled carbon nanotubes (internal diameter 1-2 nm) are the world's tiniest test tubes which allow effective entrapment of molecules in cylindrical cavities, where degrees of freedom are significantly limited. Fullerenes, for example, employed as a model molecules in previous studies have clearly demonstrated that positions, orientations, translational and rotational motions of the molecules - all are significantly influenced by the host nanotube [Acc. Chem. Res., 2005, 38, 901]. In this project, we shall expand this concept and introduce active control of the molecular behaviour, using the nanotube as a nanoscale conduit of electrons or phonons, or a nano-antenna harvesting electromagnetic radiation and transferring the energy to entrapped molecules. One of the objectives is to trigger and control reactions of the molecules, and to steer their transformations to desired products at the single-molecule level [ACS Nano, 2017, in press, http://pubs.acs.org/doi/abs/10.1021/acsnano.6b08228 ], which can potentially revolutionise the way we study chemical reactions and make materials.The approaches developed for nanotubes in this project will be transferred to molecules entrapped on graphene monolayer or within graphene bi-layer, where the principles of 1D confinement in nanotubes will be expanded and explored in 2D. In particular, intermolecular reactions leading to chain-like or ribbon-like products in 1D [Nature Mater., 2011, 10, 687] will be harnessed for molecules on graphene to construct covalent organic framework (COF) materials with bespoke structure and composition, and tuneable electronic and optical properties, thus addressing one of the most critical challenges of the graphene technology.