Calix[4]crown-based 1,3,4-Oxadiazoles as Fluorescent Chemosensors:Synthesis and Ion Recognition†

doi:10.7503/cjcu20160542

Abstract

Abstract:

Two fluorescent chemosensors, 1a and 1b, were synthesized by appending 2-phenyl-5-(2-pyridyl)-1,3,4-oxadiazole or 2,5-diphenyl-1,3,4-oxadiazole moieties on a calix[4]crown skeleton, respectively. Their molecular structures were characterized by proton and carbon nuclear magnetic resonance spectroscopy(¹H NMR and ¹³C NMR) and high resolution mass spectroscopy(HRMS). The recognition behaviors of probes 1a and 1b in CH₂Cl₂ solution to alkali metal ions(Na⁺, K⁺, Cs⁺), alkaline earth metal ions(Mg²⁺, Ca²⁺) and transition metal ions(Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Ag⁺) were investigated by UV-Vis spectrum and fluorescence spectrum. The results showed that Na⁺enhanced the fluorescence intensity of probe 1a significantly, while K⁺ and Cs⁺ only resulted in negligible changes in the fluorescence. In contrast, Ca²⁺and all the transition metal ions may quench the fluorescence greatly due to the photo-induced electron transfer mechanism. The recognition behaviors of probe 1b to alkali metal ions are similar to those of probe 1a, and com-plexation between probe 1b and the transition metal ions is weaker than that of probe 1a and the transition metal ions. The complexation has been investigated by means of ¹H NMR titration.

Key words: Calix[4]crown, 1, 3, 4-Oxadiazole, Fluorescent chemosensor, Metal ion

CLC Number:

O626.27

TrendMD:

XIE Dihuan, SUN Chun, WANG Xiaojing, HAN Jie. Calix[4]crown-based 1,3,4-Oxadiazoles as Fluorescent Chemosensors:Synthesis and Ion Recognition^†[J]. Chem. J. Chinese Universities, 2016, 37(11): 1966.

Figures/Tables 6

Scheme 1 Synthetic route of fluorescent chemosensors 1a and 1b

Fig.1 Normalized absorption spectra of probe 1a(5×10-6 mol/L) in chloroform upon addition of various metal ions(2×10-5 mol/L)

Fig.2 Fluorescence spectra changes of probe 1a(5×10-6 mol/L) in dichloromethane upon addition of various metal ions(2×10-5 mol/L)λex=280 nm.

Fig.3 1H NMR spectra of probe 1a(a), 1a+Ca2+(b), and 1a+Ca2++Na+(c) Inset: structure of probe 1a.

Fig.4 Normalized absorption spectra of probe 1b(5×10-6 mol/L) in chloroform upon addition of various metal ions(2×10-5 mol/L)

Fig.5 Fluorescence spectra changes of probe 1b(5×10-6 mol/L) in dichloromethane upon addition of various metal ions(2×10-5 mol/L)λex=280 nm.

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