Entrapment, Manipulation and Reactions of Molecules at the Nanoscale

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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.