含蒽醌基硫桥杯芳烃的点击合成及其对铝离子的荧光传感

Synthesis of Anthraquinone-Based Thiacalixarene via Click Chemistry and Its Fluorescence Sensing Towards Al^(3+)

在二甲基甲酰胺(DMF)溶剂中,下缘含端基溴的四取代硫桥[4]芳烃1和NaN_3反应得到含叠氮端基硫桥[4]芳烃衍生物2,利用点击反应,以CuSO_4/VcNa为催化剂,叠氮基硫桥[4]芳烃衍生物2和端基炔蒽醌衍生物3反应合成了以三唑基为连接的蒽醌基硫桥杯芳烃衍生物4,其通过了~1H NMR,FT-IR,MS(MALDI-TOF)和元素分析等表征.荧光光谱实验研究了化合物4对金属离子的荧光传感行为,结果表明化合物4对Al^(3+)表现出了很好的荧光响应和良好的选择性.Job实验表明4对Al^(3+)的配比为1:2;荧光滴定实验表明:在室温条件下,在CHCl_3-CH_3CN(V:V=3:1)溶剂中,4对A1^(3+)作用的键合常数K_3为2670 dm^3·mol^(-1).因此,化合物4有望作为Al^(3+)的新型荧光传感器.

Tetrabromobutoxy thiacalix[4]arene （1） was reacted with sodium azide （NAN3） in dimentylforma- mide （DMF） to obtain tetraazidobutoxy thiacalix[4]arene （2）. The sequent reaction of 2 with 1,8-bis（prop-2- ynyloxy）anthraquinone （3） catalyzed by CuSO4/VcNa to gave a novel anthraquinone-based thiacalixarene compound 4, which was characterized by 1H NMR, FT-IR, MS （MALDI-TOF） and elemental analysis. The fluorescence experiments have shown that compound 4 has a good selectivity with Al3＋ and the complexation of 4 with Al3＋ in a 1 ： 2 complex mode gives an enhanced fluorescence change at 559 nm. In CHC13-CH3CN （V ： V=3 ：1） solvent, the binding constant for the complex 4 and A13＋ is 2670 dm3·mol-1 at room temperature. Hence, compound 4 can be used as a new fluorescent sensor for the Al3＋ ion.