Tetraphenylethylene-Based Tetradentate Azolium Salts: Synthesis and Selective Recognition for Ions

doi:10.6023/cjoc202103011

Abstract

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

Cite this article

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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Fig. & Tab. 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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