Lu Zhengyu, Zhu Qin, Cai Yuanting, Chen Zhixin, Zhuo Kaiyue, Zhu Jun, Zhang Hong, Xia Haiping
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Department of Chemistry, Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518055, China.
Sci Adv. 2020 Jan 17;6(3):eaay2535. doi: 10.1126/sciadv.aay2535. eCollection 2020 Jan.
The never-ending pursuits for exploring aromatic molecular architectures result in the large libraries of aromatics with fascinating structures, which have greatly broadened the scope of aromaticity. Despite extensive efforts that have been paid to develop aromatic frameworks, the construction of polycyclic aromatics that share a bridgehead atom with more than three rings has never been accomplished. Here, an unprecedented family of aromatics, in which a metal center shared by 4 five-membered aromatic rings, has been achieved by using the metalla-click reactions with excellent yields and remarkable regioselectivity. The distinctive tetracyclic aromatics exhibit a broad absorption in the ultraviolet-visible near-infrared region and excellent thermal stability in air, enabling their potential applications in photoelectric materials and biomedicine. This study now makes it possible to incorporate four aromatic rings with one common sharing metal center by a straightforward strategy that would promote further development of previously unknown polycyclic complex motifs in aromatic chemistry.
对探索芳香分子结构的不懈追求催生了大量具有迷人结构的芳烃库，这极大地拓宽了芳香性的范畴。尽管人们为开发芳香骨架付出了诸多努力，但构建具有一个桥头原子且含三个以上环的多环芳烃却从未实现。在此，通过金属点击反应以优异的产率和显著的区域选择性实现了一个前所未有的芳烃家族，其中一个金属中心由4个五元芳香环共享。这种独特的四环芳烃在紫外-可见近红外区域表现出宽泛的吸收，且在空气中具有出色的热稳定性，使其在光电材料和生物医学领域具有潜在应用价值。这项研究现在通过一种直接的策略，使得将四个芳香环与一个共同的共享金属中心结合成为可能，这将推动芳香化学中此前未知的多环复合 motif 的进一步发展。
