Kato Masaki, Fukui Norihito, Shinokubo Hiroshi
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan.
PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, 332-0012, Japan.
Chemistry. 2022 Jan 10;28(2):e202103647. doi: 10.1002/chem.202103647. Epub 2021 Dec 7.
We report the synthesis and properties of indeno[1,2,3,4-pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon-carbon bonds. The synthetic route through two-fold C-H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium-sized aromatic hydrocarbon with the composition C H that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO-LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron-withdrawing subunit (benzoaceanthrylene) and an electron-donating subunit (perylene). The electronic properties of indenoperylene were modulated via post-functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near-infrared-responsive and redox-active materials.
我们报道了茚并[1,2,3,4-pqra]苝的合成及其性质，它是通过一个蒽单元与一个萘单元经由三个碳-碳键稠合而成。通过双重C-H芳基化的合成路线不仅能够合成未取代的茚并苝，还能以克级规模快速获得其芳基化衍生物。茚并苝是一种组成为C₁₈H₁₀的中型芳烃，与蒄同分异构。然而，由于其较小的HOMO-LUMO能隙，其吸收覆盖了整个可见光区域。此外，茚并苝尽管没有外围取代基，却表现出高稳定性。我们提出茚并苝独特的电子结构源于吸电子亚基（苯并苊烯）和供电子亚基（苝）的共存。通过区域选择性溴化的后功能化对茚并苝的电子性质进行了调控。当前的研究表明，茚并苝作为近红外响应和氧化还原活性材料的主要骨架是一个有前途的候选物。
