Structure, Luminescent Sensing and Proton Conduction of a Boiling-Water-Stable Zn(II) Metal-Organic Framework

• Main Authors: Hua-Qun Zhou, Sai-Li Zheng, Can-Min Wu, Xin-He Ye, Wei-Ming Liao, Jun He
• Format: Article
• Language: English
• Published: MDPI AG 2021-08-01
• Series: Molecules
• Subjects: proton conduction; metal ion sensing; luminescence; metal-organic framework
• Online Access: https://www.mdpi.com/1420-3049/26/16/5044

A novel Zn(II) metal-organic framework [Zn₄O(C₃₀H₁₂F₄O₄S₈)₃]_n, namely <b>ZnBPD-4F4TS</b>, has been constructed from a fluoro- and thiophenethio-functionalized ligand 2,2′,5,5′-tetrafluoro-3,3′,6,6′-tetrakis(2-thiophenethio)-4,4′-biphenyl dicarboxylic acid (<b>H₂BPD-4F4TS</b>). <b>ZnBPD-4F4TS</b> shows a broad green emission around 520 nm in solid state luminescence, with a Commission International De L’Eclairage (CIE) coordinate at x = 0.264, y = 0.403. Since d¹⁰-configured Zn(II) is electrochemically inert, its photoluminescence is likely ascribed to ligand-based luminescence which originates from the well-conjugated system of phenyl and thiophenethio moieties. Its luminescent intensities diminish to different extents when exposed to various metal ions, indicating its potential as an optical sensor for detecting metal ion species. Furthermore, <b>ZnBPD-4F4TS</b> and its NH₄Br-loaded composite, <b>NH₄Br@ZnBPD-4F4TS</b>, were used for proton conduction measurements in different relative humidity (RH) levels and temperatures. Original <b>ZnBPD-4F4TS</b> shows a low proton conductivity of 9.47 × 10⁻¹⁰ S cm⁻¹ while <b>NH₄Br@ZnBPD-4F4TS</b> shows a more than 25,000-fold enhanced value of 2.38 × 10⁻⁵ S cm⁻¹ at 40 °C and 90% RH. Both of the proton transport processes in <b>ZnBPD-4F4TS</b> and <b>NH₄Br@ZnBPD-4F4TS</b> belong to the Grotthuss mechanism with <i>E</i>_a = 0.40 and 0.32 eV, respectively.