Convex Polycycles: Synthesis, Structure, and Chemistry of Heterotriquinanes

本研究计划围绕含杂原子的凸多环化合物的合成和应用展开。该项目的主要目标是制备氮原子上不对称的氮杂喹烷用于手性H+或X+的传递，合成一系列基于氮杂奎烷的过渡金属配体和主客体体系，合成新的(O，S，P和/或B)三喹烷，三喹烯和二十五烯，通过旋三酮设计一种新的合成进入杂三喹烷环体系，以及通过杂三奎烯二聚反应和全合成来接近杂十二面体。这些研究将为研究人员提供在有机合成、配位化学、结晶学以及芳香性、应变、电子离域和分子结构基本方面的广泛经验。在化学合成计划的支持下，加州大学戴维斯分校化学系的马克·马斯卡尔教授将探索具有曲面的分子的本质--从凹面到半球形，再到完全封闭的壳层多面体。对这种分子的研究回答了有关有机(碳基)材料的电子结构的基本问题，也提供了实际应用的机会，特别是在纳米技术领域。该项目还为基础和应用化学合成方面的研究生和博士后研究人员提供了一个极好的培训基地。该计划的更广泛影响包括通过美国化学协会SEED和加州大学戴维斯分校青年学者计划赞助暑期研究项目，发展创新的学生学习和评估实践，参与促进环太平洋地区代表性不足群体参与的计划，以及加强研究化学在本科实验室课程中的相关性。最后，正在研究的弧形和球状分子的视觉冲击力和美丽的对称性使其有更多的机会通过大众媒体和公共科学场所进行推广，从而更好地欣赏技术艺术。

This research program is based around the synthesis and applications of heteroatom-containing, convex polycycles. The principal goals of the project are to prepare azatriquinanes which are asymmetric at the nitrogen atom for applications to chiral H+ or X+ delivery, to produce a range of azatriquinane-based transition metal ligands and host-guest systems, to synthesize new series of hetero (O, S, P, and/or B) triquinanes, triquinacenes, and acepentalenes, to devise a new synthetic entry into the heterotriquinane ring system via cyclononatrione, and to approach heterododecahedranes both by heterotriquinacene dimerizations and by total synthesis. These investigations will provide the researchers with broad experience in organic synthesis, coordination chemistry, crystallography, and fundamental aspects of aromaticity, strain, electron delocalization, and molecular architecture.With the support of this award from the Chemical Synthesis Program, Professor Mark Mascal of the Department of Chemistry at the University of California Davis will explore the nature of molecules with curved surfaces -- from concave, to hemispherical, to completely closed-shell, polyhedral bodies. The study of such molecules answers fundamental questions regarding the electronic structure of organic (carbon-based) materials, and also presents opportunities for practical applications, particularly in the area of nanotechnology. This project also serves as an excellent training ground for graduate and postdoctoral researchers in fundamental and applied chemical synthesis. The broader impacts of this program include K-12 outreach by sponsoring summer research projects via the American Chemical Society SEED and UC Davis Youth Scholar Programs, the development of innovative student learning and assessment practices, involvement in programs which promote the participation of underrepresented groups in the Pacific Rim, and enhancing the relevance of research chemistry in undergraduate laboratory courses. Finally, the visual impact and beautiful symmetry of the curved and spherical molecular bodies being studied lends itself to additional outreach opportunities through the popular press and public science venues, and thereby a greater appreciation of the art of technology.