我室夏海平教授在 Nature Communications 上发表论文：Synthesis of metalla-dual-azulenes with fluoride ion recognition properties

摘要：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_π-p_π and p_π-p_π 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 ⁿBu₄NF, 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.

文章链接：https://www.nature.com/articles/s41467-023-41250-5