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

ABSTRACT: 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.

SUBMITTER: Liu HC

PROVIDER: S-EPMC10495402 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

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

Liu Hai-Cheng HC Ruan Kaidong K Ma Kexin K Fei Jiawei J Lin Yu-Mei YM Xia Haiping H

Nature communications 20230911 1

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 dπ-pπ and pπ-pπ 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-contai ...[more]

PMID: 37696902

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Project description:Rapid and efficient analysis of fluoride ion is crucial to providing key information for fluoride ion hazard assessment and pollution management. In this study, we synthesized one symmetrical structure called 1,4-bis(4,5-diphenyl-1H-imidazol-2-yl)benzene (1a) and two asymmetrical structures, namely 2-(4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-1H-phenanthro(9,10-d)imidazole (1b) and 2-(4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-1H-imidazo(4,5-f)(1,10)phenanthroline (1c), which served as an efficient anion sensor for fluoride ion over a wide range of other anions (Cl-, Br-, I-, NO₃-, ClO₄-, HSO₄-, BF₄-, and PF₆-) owing to imidazole group in the main backbone. The absorption intensity of compound 1a at λmax 358 nm slightly decreased; however, a new band at λmax 414 nm appeared upon the addition of fluoride ion, while no evident change occurred upon the addition of eight other anions. The photoluminescence intensity of compound 1a at λmax 426 nm was nearly quenched and fluorescence emission spectra were broadened when fluoride ion was added into dimethyl sulfoxide (DMSO) solution of compound 1a. Compared with the optical behaviors of the DMSO solution of compound 1a in the presence of Bu₄N⁺F-, compounds 1b and 1c exhibited considerable sensitivity to fluoride ion due to the increase in coplanarity. Furthermore, compared with the fluorescence emission behaviors of the DMSO solutions of compounds 1a and 1b in the presence of Bu₄N⁺F-, compound 1c exhibited the most significant sensitivity to fluoride ion due to the charge transfer enhancement. Consequently, the detection limits of compounds 1a-1c increased from 5.47 × 10-6 M to 4.21 × 10-6 M to 9.12 × 10-7 M. Furthermore, the largest red shift (75 nm) of the DMSO solution compound 1c in the presence of fluoride ion can be observed. Our results suggest that the increase in coplanarity and the introduction of electron-withdrawing groups to the imidazole backbone can improve the performance in detecting fluoride ion.

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

Publications

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

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