Turley Andrew T, Saha Promeet K, Danos Andrew, Bismillah Aisha N, Monkman Andrew P, Yufit Dmitry S, Curchod Basile F E, Etherington Marc K, McGonigal Paul R
Department of Chemistry, Durham University, Lower Mountjoy, Stockton Road, Durham, DH1 3LE, UK.
Department of Physics, Durham University, Lower Mountjoy, Stockton Road, Durham, DH1 3LE, UK.
Angew Chem Int Ed Engl. 2022 Jun 13;61(24):e202202193. doi: 10.1002/anie.202202193. Epub 2022 Apr 13.
Herein, we expose how the antagonistic relationship between solid-state luminescence and photocyclization of oligoaryl alkene chromophores is modulated by the conjugation length of their alkenyl backbones. Heptaaryl cycloheptatriene molecular rotors exhibit aggregation-induced emission characteristics. We show that their emission is turned off upon breaking the conjugation of the cycloheptatriene by epoxide formation. While this modification is deleterious to photoluminescence, it enables formation of extended polycyclic frameworks by Mallory reactions. We exploit this dichotomy (i) to manipulate emission properties in a controlled manner and (ii) as a synthetic tool to link together pairs of phenyl rings in a specific sequence. This method to alter the tendency of oligoaryl alkenes to undergo photocyclization can inform the design of solid-state emitters that avoid this quenching mechanism, while also allowing selective cyclization in syntheses of polycyclic aromatic hydrocarbons.
在此，我们揭示了寡芳基烯烃发色团的固态发光与光环化之间的拮抗关系是如何通过其烯基主链的共轭长度来调节的。七芳基环庚三烯分子转子具有聚集诱导发光特性。我们表明，通过环氧化物形成破坏环庚三烯的共轭时，其发射会被关闭。虽然这种修饰对光致发光有害，但它能够通过马洛里反应形成扩展的多环框架。我们利用这种二分法：（i）以可控方式操纵发射特性；（ii）作为一种合成工具，以特定序列将成对的苯环连接在一起。这种改变寡芳基烯烃进行光环化倾向的方法，可为避免这种猝灭机制的固态发光体设计提供参考，同时也能在多环芳烃合成中实现选择性环化。
