EAGER: Dimerization of Heterotriquinacenes to Heterododecahedranes

在这个由化学系化学合成项目资助的项目中，加州大学戴维斯分校化学系的Mark Mascal教授正在探索具有曲面的新分子的生产。这种方法包括利用光将两个碗状分子连接成十二面体的产物，十二面体是柏拉图固体的一种。这项研究有可能改变化学家合成球形分子的方法，这可能在包括应用材料科学和纳米技术在内的其他科学分支中具有深远的应用。研究生作为助教参与化学海外研究项目。研究人员参加了加州大学的专业发展计划，来自代表性不足群体的本科生研究人员参加了实践研究活动。该项目包括三种不同的方法来影响光化学允许的三醌和/或杂三醌二聚成十二面体烷/杂十二面体烷。第一种方法是利用水悬浮液中环加成反应的聚集效应，通过对水腔内的组分施加压力，可以显著提高反应速率。第二种方法是将基于阳离子的两亲三醌与水溶性阴离子的三醌配对，并将阳离子组织在空气/水界面上。强离子配对和疏水性可以使组分以正确的方向聚集在一起进行二聚化。最后，一种晶体工程方法也被采用，这种方法可以诱导三苯二烯在足够紧密接触的凹点上定向，从而允许拓扑化学（固态）二聚化。更广泛的影响包括培养学生进行跨学科研究，包括有机合成、光化学、理论化学和纳米技术。来自不同种族的学生研究人员参与了这个项目的各个层面。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

In this project, funded by the Chemical Synthesis Program of the Division of Chemistry, Professor Mark Mascal of the Department of Chemistry at the University of California Davis is exploring the production of new molecules that have curved surfaces. The approach involves the use of light to join two bowl-shaped molecules into products that are in the shape of a dodecahedron, one of the Platonic solids. This research has the potential to change the way chemists approach the synthesis of spherical molecules, which can have far-reaching applications in other branches of science including applied material science and nanotechnology. Graduate students are involved as teaching assistants in a chemistry study-abroad program. The researchers participate in a University of California Professional Development Program and undergraduate researchers from underrepresented groups participate in hands-on research activities. The project consists of three separate approaches to effecting the photochemically-allowed dimerization of triquinacenes and/or heterotriquinacenes to dodecahedranes/heterododecahedranes. The first approach involves the use of aggregation effects on cycloaddition reactions in water suspensions, which can dramatically increase rates by exerting pressure on the components within aqueous cavities. A second approach is to pair a triquinacenium cation-based amphiphile with a water-soluble, anionic triquinacene and organize the cation at the air / water interface. Strong ion pairing and hydrophobic forces may bring the components together in the right orientation for dimerization. Finally, a crystal engineering approach is also being adopted which may induce triquinacenes to orient with concavities in sufficiently close contact to allow topochemical (solid state) dimerization. The broader impacts include training students in interdisciplinary research encompassing organic synthesis, photochemistry, theoretical chemistry, and nanotechnology. Student researchers from a broad representation of ethnicities are engaged at all levels in this project.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.