基于四苯乙烯的四齿唑盐: 合成和对离子的选择性识别

doi:10.6023/cjoc202103011

摘要/Abstract

合成和表征了两种新型的基于四苯基乙烯的四齿唑盐: 1,1,2,2-四[(2'-(N-甲基咪唑-1-基)乙氧基苯基)]乙烯六氟磷酸盐(1)和1,1,2,2-四[(2'-(N-吡啶甲基苯并咪唑-1-基)乙氧基苯基)]乙烯六氟磷酸盐(2)通过荧光光谱, UV/vis光谱, HRMS, ¹H NMR和红外光谱研究了1对阴离子和2对阳离子的识别性能. 结果表明: 通过荧光方法, 1能够将 $H_{2}PO_{4}^-$与其他阴离子区分开, 2能够将Ag⁺与其他阳离子区分开.

关键词: 四苯乙烯, 唑盐, 荧光, 识别, 离子

Two new tetraphenylethylene-based tetradentate azolium salts, 1,1,2,2-tetrakis{[2'-(N-methyl-imidazolium-1-yl)ethoxyl]phenyl}ethylene hexafluorophosphate (1) and 1,1,2,2-tetrakis{[2'-(N-picolyl-benzimidazolium-1-yl)ethoxyl]phenyl}ethylene hexafluorophosphate (2), were synthesized and characterized. Recognitions of 1 for anions and 2 for cations were studied through fluorescence spectra, UV/vis spectra, HRMS, ¹H NMR and infrared spectroscopies. The results revealed that 1 was able to differentiate $H_{2}PO_{4}^-$ from other anions, and 2 was able to differentiate Ag⁺ from other cations via fluorescence method.

Key words: tetraphenylethylene, azolium salts, fluorescence, recognition, ions

引用此文

李芯颖, 赵志翔, 胡林海, 魏登澈, 柳清湘. 基于四苯乙烯的四齿唑盐: 合成和对离子的选择性识别[J]. 有机化学, 2021, 41(9): 3608-3616.

Xinying Li, Zhixiang Zhao, Linhai Hu, Dengche Wei, Qingxiang Liu. Tetraphenylethylene-Based Tetradentate Azolium Salts: Synthesis and Selective Recognition for Ions[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3608-3616.

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图/表 11

Scheme 1. Preparation of tetradentate azolium salts 1 and 2

Figure 1. Fluorescent spectra of 1 (1×10–6 mol/L) with 5.0 equiv. of $HPO_{4}^-$, NO3–, $H_{2}PO_{4}^-$, OAc–, I–, F–, Br– and Cl– in EtOH/DMSO (V∶V=99∶1) at room temperature

Figure 2. Fluorescent titration of 1 (1.0×10–6 mol/L) with diverse $C_{H_{2}PO_{4} ^-}$ in EtOH/DMSO (V∶V=99∶1) at room temperature $C_{H_{2}PO_{4} ^-}$of curves 1~28 are 0, 0.04, 0.07, 0.11, 0.17, 0.25, 0.33, 0.43, 0.5, 0.67, 0.8, 1.0, 1.25, 1.5, 1.75, 2.0, 2.3, 2.6, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.5, 11.0×10–6 mol/L (from bottom to top). Inset: the curve of F/F0 vs $C_{H_{2}PO_{4} ^-}$ at 400~600 nm

Figure 3. UV/vis titration of 1 (1.0×10–5 mol/L) with diverse $C_{H_{2}PO_{4}^-}$ in EtOH/DMSO (V∶V=99∶1) in room temperature $C_{H_{2}PO_{4} ^-}$of curves 1~16 are 0, 0.03, 0.08, 0.12, 0.19, 0.28, 0.45, 0.69, 0.8, 1.27, 1.8, 2.75, 3.6, 4.5, 5.5, 6.0×10–5 mol/L (from bottom to top). Inset: Job's plot of 1•2 $H_{2}PO_{4} ^-$

Scheme 2. Intramolecular binding mode of 1 with $H_{2}PO_{4} ^-$

Figure 4. Fractional 1H NMR spectra using DMSO-d6 as solvent (i) Pure 1; (ii) 0.25 equiv. of $H_{2}PO_{4} ^-$ and 1; (iii) 0.5 equiv. of $H_{2}PO_{4} ^-$ and 1; (iv) 0.75 equiv. of $H_{2}PO_{4} ^-$ and 1; (v) 1.0 equiv. of $H_{2}PO_{4} ^-$ and 1; (vi) 1.25 equiv. of $H_{2}PO_{4} ^-$ and 1; (vii) 1.5 equiv. of $H_{2}PO_{4} ^-$ and 1; (viii) 2.0 equiv. of $H_{2}PO_{4} ^-$ and 1; (ix) 2.5 equiv. of $H_{2}PO_{4} ^-$ and 1

Figure 5. Fluorescence spectra for 2 (1.0×10–6 mol/L) with salts (30.0 equiv.) of Ag+, Na+, NH4+, Li+, K+, Ca2+, Co2+, Cd2+, Ni2+, Cu2+, Pb2+, Zn2+, Al3+and Cr3+ in EtOH/DMSO (V∶V=99∶1) at 400~600 nm in room temperature

Figure 6. Fluorescence titration for 2 (1.0×10–6 mol/L) with different cAg+ in EtOH/DMSO (V∶V=99∶1) at 400~600 nm in room temperature cAg+ of curves 1~25 are 0, 0.02, 0.07, 0.13, 0.2, 0.28, 0.36, 0.45, 0.65, 0.8, 1.1, 1.4, 2.0, 2.6, 3.0, 4.0, 6.0, 10.0, 14.0, 18.0, 20.0, 22.0, 27.0, 30, 33×10–6 mol/L (from bottom to top). Inset: the curve of F/F0 vs cAg+ at 465 nm

Figure 7. Ultraviolet spectra for 2 (1.0×10–6 mol/L) with different cAg+ in EtOH/DMSO (V∶V=99∶1) in room temperature cAg+ for curves 1~38 are 0, 0.04, 0.07, 0.11, 0.17, 0.25, 0.33, 0.43, 0.5, 0.6, 0.8, 1.0, 1.2, 1.5, 1.7, 2.3, 3, 4, 5, 7, 9, 10, 13, 17, 20, 23, 27, 30, 33, 36, 39, 42, 45, 50, 55, 60, 65 and 70×10–6 mol/L (from bottom to top). Inset: Job's plot for 2•2Ag+

Figure 8. Fractional 1H NMR spectra using DMSO-d6 as solvent (i) 2; (ii) adding 0.25 equiv. of Ag+ to 2; (iii) adding 0.5 equiv. of Ag+ to 2; (iv) adding 0.75 equiv. of Ag+ to 2; (v) adding 1.0 equiv. of Ag+ to 2; (vi) adding 1.25 equiv. of Ag+ to 2; (vii) adding 1.5 equiv. of Ag+ to 2; (viii) adding 1.75 equiv. of Ag+ to 2; (ix) adding 2.0 equiv. of Ag+ to 2; (x) adding 2.5 equiv. of Ag+ to 2

Scheme 3. Intramolecular binding mode of 2 with Ag+

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