Molecular Plasmonic Devices for Writing at the Nanoscale

21世纪的化学家能够以一种过去几代人做梦也想不到的方式操纵原子和分子。今天，我们可以在分子水平上构建处理（读和写）信息的设备。就像它们的宏观对应物一样，分子级设备需要能量来运行，并需要信号来与操作员通信。光是最便宜、最丰富、最吸引人的读写信息的工具，使我们能够在本地或远程、无创和负担得起的实验装置上完成这项工作。然而，衍射阻止了超小体积内的光聚焦，因此，使用传统照明技术制造具有分子精度的特征。我们的最终目标是通过将有机分子和金属纳米粒子结合在一起，使它们的特性可以协同使用，从而克服衍射势垒并在亚衍射状态下操纵光。这些巧妙的策略提供了将化学反应限制在纳米尺度内的机会，并以可持续的方式以前所未有的分辨率制造特征。在一个使用纳米技术发明高性能、节能和可回收材料的世界里，将经典的有机化学与新的、令人兴奋的等离子体技术相结合，有可能绕过衍射的限制，为通信和计算机行业方便地制造小型化物体。

The chemists of the 21st century can manipulate atoms and molecules in a way that past generations could not even dream about. Today we can construct devices for the processing (reading and writing) of information at the molecular level. Like their macroscopic counterparts, molecular-level devices need energy to operate, and signals to communicate with the operator. Light is the most inexpensive, abundant and attractive tool to read and write information, allowing us to do this locally or remotely, noninvasively and with affordable experimental setups. However, diffraction prevents the focusing of light within ultra-small volumes and, as a result, the fabrication of features with molecular precision using conventional illumination techniques. Our ultimate goal is to overcome the diffraction barrier and to manipulate light in the subdiffraction regime, by engineering together organic molecules and metal nanoparticles such that their properties can be used cooperatively. These ingenious strategies offer the opportunity to confine chemical reactions within nanoscaled volumes and to fabricate features with unprecedented resolution, in a sustainable fashion. Combining classic organic chemistry with new, exciting, plasmonic technology has the potential to bypass the limitations of diffraction and permit the convenient fabrication of miniaturized objects for the communications and computer industries, in a world that uses nanotechnology to invent high performance, energy efficient, and recyclable materials. The main objective of this research plan is the preparation of organic substrates for plasmonic activation by metal nanoparticles for fluorescence patterning at the nanoscale. Initial work will focus on (1) the synthetic potential for plasmon-mediated chemical reactions driven by light excitation of nanoparticles, which will be exploited to convert fluorogenic organic substrates into emissive products. Toward the realization of the main objective, metal nanostructures will also be exploited in (2) plasmonic multiphoton photochemical processes. In addition to implementing new protocols in nanotechnology, this research line will lead to the development and the understanding of innovative systems with the capability of performing complex and serial functions. Combining multiple discrete components into a single multifunctional nanomaterial would be useful in a variety of applications, particularly in cascade-like reactions; the exploration of the combinatorial properties of metal nanostructures will offer exciting opportunities for high-impact discoveries in materials design. Through innovative and challenging research, HQP will acquire diverse technical and interpersonal skill sets that will prepare them to pursue careers in academia, industry or public service, and to make significant contributions to the future of Canadian science and innovation.