乙二胺类环三磷腈衍生物的合成及荧光检测Cu^(+)的应用  

Synthesis and spectral properties of ethylenediamine cyclic triphosphazene derivatives

作　　者：张向东 左胜利 刘建军 朱腾飞 ZHANG Xiangdong;ZUO Shengli;LIU Jianjun;ZHU Tengfei(College of Chemistry,Beijing University of Chemical Technology,Beijing 100029,China)

机构地区：[1]北京化工大学化学学院,北京100029

出　　处：《化学研究》2023年第3期225-230,共6页Chemical Research

基　　金：国家自然科学基金资助项目(11172043)。

摘　　要：以氮磷交替结构为骨架的环磷腈化合物通过具有荧光特性的可控侧基取代,可实现对环境中金属阳离子的高选择性荧光识别。本文通过在N_(3)P_(3)(O_(2)C1_(2)H_(8))Cl_(4)(1)和N_(3)P_(3)(O_(2)C1_(2)H_(8))_(2)Cl_(2)(2)上引入N,N′-二甲基乙二胺、N,N′-二苯基乙二胺与N,N′-二苄基乙二胺,合成了以(2,2′-联苯二酚氧基)1(N,N′-二甲基乙二胺基)2环三磷腈为代表的系列新型化合物,通过^(1)H NMR、^(13)C NMR与质谱确定了化合物的结构,其产率从61%到94%。荧光性质研究表明不同浓度Cu^(+)对具有不同吸电子能力二胺类取代化合物的荧光产生荧光衰减现象,且N_(3)P_(3)(O_(2)C1_(2)H_(8))_(1)(C_(4)H_(10)N_(2))_(2)在0~8×10^(-6)mol/L的离子浓度范围内具有良好的线性响应,这可归因于该类化合物磷腈主链的结构特殊性及取代基中多氮原子的存在,其吸收光谱和荧光光谱对Cu^(+)浓度变化非常敏感,且量子产率也优于传统席夫碱取代的环磷腈化合物,使得此类荧光量子探针在未来具有良好的应用价值。Cyclophosphazene compounds with alternating nitrogen and phosphorus structure as skeleton can realize highly selective fluorescent recognition of metal cations in the environment through the substitution of controllable side groups with fluorescent properties.N,N′-dimethylethylenediamine,N,N′-diphenylethylenedia-mine and N,N′-dibenzylethylenediamine,a new series of(2,2′-biphenoloxy)1-(N,N′-dimethylethylenediamino)2-cyclotriphosphazene were synthesized,the structures of the compound were determined by^(1)H NMR,^(13)C NMR and mass spectrometry,and the yields ranged from 61%-94%.The study of fluorescence properties show that different concentrations of Cu+have different electron-withdrawing abilities with diamine substitutions the fluorescence of the compounds produces fluorescence decay phenomenon,respectively,and N_(3)P_(3)(O_(2)C_(12)H_(8))1(C_(4)H_(10)N_(2))2 has a good linear response in the ionic concentration range of 0-8×10^(-6)mol/L,which can be attributed to the particularity of the phosphazene main chain of these compounds and the existence of substituent polynitrogen atoms.Its absorption and fluorescence spectra are very sensitive to the change of Cu^(+)concentration,and the quantum yield is also better than that of traditional cyclophosphazene compounds substituted by Schiff base.Its high sensitivity and low detection limit make this fluorescent-like quantum probes have valuable application in the future.

关 键 词：环三磷腈 亲核取代 乙二胺 荧光 

分 类 号：O626[理学—有机化学]