The development and mechanistic understanding of solid-state reactivity for energy- and materials-efficient synthesis

提出的研究旨在了解和发展固态反应，作为实现清洁、环保的化学合成的手段，开发新的二氧化碳封存材料，并引入在溶液中难以或不可能发生的化学反应。发展更清洁、更安全、更有效的合成方法是现代化学的核心挑战之一。在这种情况下，无溶剂机械化学（即由机械研磨或铣削引起的化学转化）已经显示出可以匹配甚至超过传统溶液化学的合成潜力。在实现更清洁、更节能的化学反应的同时，机械化学也为以前被认为很难、甚至不可能实现的化学反应和产物打开了大门。我们的团队一直处于这一发展的前沿，特别是在用于气体储存的微孔金属有机框架（mof）的合成，开发活性药物成分（api）的新路线，以及引入机械化学反应的实时机制研究的第一个技术。

The proposed research is aimed towards understanding and developing solid-state reactivity as a means of achieving clean, environmentally-friendly chemical synthesis, developing new materials for sequestration of carbon dioxide, and introducing chemical reactions that are difficult or not possible in solution. The development of cleaner, safer and more efficient synthetic methodologies is one of the central challenges of modern chemistry. In that context, solvent-free mechanochemistry (i.e. chemical transformations induced by mechanical grinding or milling) has revealed synthetic potential that can match, and even exceed that of conventional solution chemistry. While enabling cleaner, more energy-efficient reactivity, mechanochemistry also opens access to chemical reactions and products that have previously been thought difficult, or even impossible to achieve. Our group has been at the cutting edge of this development, especially in the synthesis of microporous metal-organic frameworks (MOFs) for gas storage, developing new routes to active pharmaceutical ingredients (APIs), and introducing the first techniques for real-time mechanistic studies of mechanochemical reactions. However, despite such rapid growth, mechanochemistry and related solid-state reaction techniques still remain poorly understood, with a lack of mechanistic understanding and reaction energetics limiting its further development. We will address this challenge by building on our unique expertise in real-time, in situ reaction monitoring of mechanochemical reactions, to develop new techniques that will give us a detailed understanding of mechanochemistry in terms of changes in bulk reactant structure, as well as changes in molecular structure and environment. These new diffraction, spectroscopic and thermal techniques will be used along with computational modelling to advance the synthesis and understanding of MOFs, as well as to develop new organic transformations. The deliverables will be advances in mechanochemistry and solvent-free reactivity, development of MOFs designed not only for porosity, but also for stability, as well as new coupling reactions of amides and amino acids, important starting materials in pharmaceuticals and chemical industry. We will develop new directions in solvent-free chemistry, notably the coupling of mechano- and photochemistry, and enzyme catalysis under milling conditions. Offering the solid state as a completely new medium for enzyme activity could revolutionize biomass processing, and we will develop such solvent-free enzyme catalysis for the breakdown of recalcitrant biomass polymers chitin and lignin. The outcomes of proposed research will be major milestones in developing methods and materials for sustainable and clean chemistry, and will greatly contribute to the position of Canada as a leader in chemical innovation and manufacturing.