Leith Gabrielle A, Rice Allison M, Yarbrough Brandon J, Kittikhunnatham Preecha, Mathur Abhijai, Morris Nicholas A, Francis Megan J, Berseneva Anna A, Dhull Poonam, Adams Richard D, Bobo M Victoria, Vannucci Aaron A, Smith Mark D, Garashchuk Sophya, Shustova Natalia B
Department of Chemistry and Biochemistry, University of South Carolina Columbia South Carolina 29208 USA
Chem Sci. 2021 Apr 8;12(19):6600-6606. doi: 10.1039/d0sc06755e.
Unprecedented one-step C[double bond, length as m-dash]C bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between "open" corannulene and a strong electron acceptor such as 7,7,8,8-tetracyanoquinodimethane. Alternative to a one-pot solid-state corannulene "unzipping" route, we reported a nine-step solution-based approach for preparation of novel planar "open" corannulene-based derivatives in which electronic structures and photophysical profiles were estimated through the energies and isosurfaces of the frontier natural transition orbitals.
报道了前所未有的一步法碳-碳双键断裂导致巴基碗（π碗）开口，这可能提供通往具有以前无法获得的拓扑结构的富碳结构的途径；突出了与用于多环芳烃的传统方法相比，实施截然不同的合成路线来制备π碗的可能性。通过理论建模，我们评估了π碗平面化可行的机理途径以及可能影响这种转变的因素，包括应变和释放能。通过运用马库斯理论、光谱学和晶体学分析，我们估计了“开放”的碗烯与强电子受体如7,7,8,8-四氰基对苯二甲烷之间电荷转移和电子耦合的可能性。作为一锅固态碗烯“解拉链”路线的替代方法，我们报道了一种基于溶液的九步法，用于制备新型平面“开放”碗烯基衍生物，其中通过前沿自然过渡轨道的能量和等值面来估计其电子结构和光物理特征。
