Acid-base Vapor Sensing Enabled by ESIPT-attributed Cd(II) Coordination Polymer with Switchable Luminescence
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doi: 10.1007/s40242-020-0039-9
Article
Acid-base Vapor Sensing Enabled by ESIPT-attributed Cd(II) Coordination Polymer with Switchable Luminescence FU Pengyan1, MO Junting1, SUN Sisi1, YIN Shaoyun2, WANG Haiping3 and PAN Mei1* 1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, P. R. China; 2. Analysis and Test Center, Guangdong University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, P. R. China; 3. School of Biotechnology and Health Sciences, Wuyi University, Jiangmen 529020, P. R. China Abstract Fluorescence materials based on excited state intramolecular proton transfer(ESIPT) have attracted great attention due to the unique four-level energy states. Herein, we report the assembly of a Cd-LF coordination polymer from purposely designed LF(H2hpi2cf) ligand, which can present switchable luminescence behavior by gain or loss protons originated in uncoordinated ESIPT sites and serve as acid-base vapor sensors. Fabricated into in-situ grown film or transparent ink by simple methods, Cd-LF presents facile and portable amine sensor for food spoilage detection and fluorescent anti-counterfeiting ink applications. Keywords Excited state intramolecular proton transfer; Coordination polymer; Acid-base vapor; Fluorescence sensor; Anti-counterfeiting ink
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Introduction
Excited state intramolecular proton transfer(ESIPT), as a prototype mechanism in fluorescence and related molecules, has attracted the scientist great attention in recent years[1,2]. ESIPT molecules have unique four-level energy states(E→E*→K*→K), leading to uniquely large Stokes’ shifted fluorescence without self-reabsorption, and dual emissions with spectral sensitivity to the surrounding environment. Therefore, these materials have wide applications in various fields including organic light emitting diode(OLED)[3,4], lasing[5―9], fluorescence imaging[10―14], sensing[12―15], and so on. Among them, the fluorescence responsiveness of ESIPT materials to the surrounding environment makes them potential sensors for acid-base, temperature, anions and solvents, etc.[16―19]. Although pure organic ESIPT molecules have been examined as fluorescent sensors in solution, solid-state fluorescent sensors and films based on ESIPT-attributed coordination complexes have not been sufficiently developed. For this purpose, the ligand should be properly designed to have separated coordination sites from ESIPT sites, and can remain the excited state proton transfer attribute after coordination with metals[20―22]. Herein, we report a novel Cd-LF coordination polymer for
detection of acid-base vapors, which is self-assembled by LF(H2hpi2cf) ligand with Cd(II) ions. The ―OH···N sites on the ligands are not coordinated, leaving availability for ESIPT involved fluorescence-tuning responsiveness. Cd-LF can regulate the ESIPT process by gain or loss protons of the ESIPT sites, thus showing different emission in the atmosphere of acid and basic va
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