Synthesis of metalla-dual-azulenes with fluoride ion recognition properties

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 skel...

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Bibliographic Details
Published in:Nature communications 2023-09, Vol.14 (1), p.5583-10, Article 5583
Main Authors: Liu, Hai-Cheng, Ruan, Kaidong, Ma, Kexin, Fei, Jiawei, Lin, Yu-Mei, Xia, Haiping
Format: Article
Language:English
Subjects:
119/118
140/131
140/58
639/638/263/406/910
639/638/403/933
639/638/911/406/910
Azulene
Chemical reactions
Fluorides
Humanities and Social Sciences
Metals
multidisciplinary
Organic chemistry
Photoelectricity
Recognition
Science
Science (multidisciplinary)
Transition metals
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Summary: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 n Bu 4 NF, 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. Azulene-based conjugated systems are of great interests due to their unusual structures and photophysical properties but incorporation of a transition metal into azulene skeleton presents remains elusive. Here, the authors describe an efficient [5 + 2] annulation reaction for the rapid construction of a metalla-dual-azulene.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-023-41250-5