Liu Hai-Cheng, Ruan Kaidong, Ma Kexin, Fei Jiawei, Lin Yu-Mei, Xia Haiping
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, Fujian, China.
Department of Chemistry, Shenzhen Grubbs Institute, Southern University of Science and Technology, 518055, Shenzhen, China.
Nat Commun. 2023 Sep 11;14(1):5583. doi: 10.1038/s41467-023-41250-5.
Azulene-based conjugated systems are of great interests due to their unusual structures and photophysical properties. Incorporation of a transition metal into azulene skeleton presents an intriguing opportunity to combine the d-p and p-p conjugated properties. No such metallaazulene skeleton however has been reported to date. Here, we describe our development of an efficient [5 + 2] annulation reaction to rapid construction of a unique metal-containing [5-5-7] scaffold, termed metalla-dual-azulene (MDA), which includes a metallaazulene and a metal-free organic azulene intertwined by sharing the tropylium motif. The two azulene motifs in MDA exhibit distinct reactivities. The azulene motif readily undergoes nucleophilic addition, leading to N-, O- and S-substituted cycloheptanetrienyl species. Demetalation of the metallaazulene moiety occurs when it reacts with BuNF, which enables highly selective recognition of fluoride anion and a noticeable color change. The practical [5 + 2] annulation methodology, facile functional-group modification, high and selective fluoride detection make this new π-conjugated polycyclic system very suitable for potential applications in photoelectric and sensing materials.
基于薁的共轭体系因其独特的结构和光物理性质而备受关注。将过渡金属引入薁骨架为结合d-p和p-p共轭性质提供了一个有趣的机会。然而，迄今为止尚未报道过此类金属薁骨架。在此，我们描述了一种高效的[5 + 2]环化反应的开发，用于快速构建一种独特的含金属[5-5-7]支架，称为金属双薁（MDA），它包括一个金属薁和一个无金属的有机薁，通过共享环庚三烯正离子基序相互交织。MDA中的两个薁基序表现出不同的反应性。薁基序容易发生亲核加成反应，生成N-、O-和S-取代的环庚三烯基物种。当金属薁部分与BuNF反应时会发生脱金属反应，这使得能够对氟阴离子进行高选择性识别并伴有明显的颜色变化。实用的[5 + 2]环化方法、简便的官能团修饰、高选择性氟化物检测使得这种新的π共轭多环体系非常适合在光电和传感材料中的潜在应用。
