Novel Catalytic Transformations of Organoboron Species and the Development of Ultrastable Self-Assembled Monolayers on Metal Surfaces

这项拟议的研究是基于我们实验室的两项令人兴奋的发现。2014年，我们证明了NHC在黄金上形成了单分子膜，可以经受前所未有的极端高温、氧化剂、酸和碱。这项工作被包括芬兰纳米科学中心主任哈基宁在内的国际专家称为“改变游戏规则”。其他专家称其为“新金本位”和“高雅”。已知NHC在过渡金属络合物中形成强键，但以前还没有被研究过作为金属表面自组装单分子膜的硫醇替代品。在这个提议中，我们将探索这一新颖而令人兴奋的发现的许多方面，包括：(1)NHC结构对薄膜质量和结合强度的影响，(2)NHC用于在包括银和铜在内的其他金属上成膜，其中NHC涂层可以帮助防止氧化和变色，以及(3)NHC在幻数Au团簇中的使用，这是一种了不起的分子材料，主要是用硫醇配体制备的，因此NHCS将提供一种全新的纳米材料。在长期目标中，我们将(4)探索NHC在分子电子学中的应用，以及作为催化活性表面和纳米颗粒的修饰剂。该项目的许多合作项目已经到位，包括与Horton(表面科学，皇后)，McLean(STM成像，女王物理学)，Baddeley(STM成像，圣安德鲁斯)，Kraatz(电化学，T SCAR大学)，Häkkinen(理论，芬兰)，Mosey(理论，皇后)和Tsukuda(纳米团，日本)。

The proposed research is based on two exciting discoveries from our lab. In 2014, we demonstrated that NHCs form monolayers on gold that withstand unprecedented extremes of heat, oxidant, acid and base. This work was called "game changing" by international experts, including Häkkinen, director of the Nanoscience Centre in Finland. Other experts called it "the new gold standard" and "elegant". NHCs have been known to form strong bonds in transition metal complexes but had not previously been examined as alternatives to thiols for self-assembled monolayers on metals. In this proposal, we will explore many aspects of this novel and exciting discovery, including: (1) the effect of NHC structure on film quality and bond strength, (2) the use of NHCs to form films on other metals including Ag and Cu where the NHC coating may help prevent oxidation and tarnishing, and (3) the use of NHCs in magic number Au clusters, which are remarkable molecular materials, that have been largely prepared with thiol ligands and thus NHCs will provide a completely new type of nanomaterial. In long term goals, we will (4) explore the use of NHCs in molecular electronics and as modifiers for catalytically active surfaces and nanoparticles. Many collaborations for this project are already in place, including with Horton (surface science, Queen's), McLean (STM imaging, Queen's Physics), Baddeley (STM imaging, St. Andrews), Kraatz (Electrochemistry, U of T Scar.), Häkkinen (Theory, Finland), Mosey (Theory, Queen's) and Tsukuda (nanoclusters, Japan).