固体三芳基硼-相变材料可调比率荧光温度计

温度响应相变材料(PCMs)的微区黏度和自由体积等性质在熔点附近会发生可逆且快速的变化,这种变化可以放大荧光探针的响应性.本文合成了2个对高黏度具有比率响应发光的新型三芳基硼化合物4-(1-{4-[双(4-溴-2,3,5,6-四甲基苯基)硼烷基]-2,3,5,6-四甲基苯基}哌啶-4-基)吗啉(MPDB1)和4,4-({[(4-溴-2,3,5,6-四甲基苯基)硼烷二基]双(2,3,5,6-四甲基-4,1-亚苯基)}双(哌啶-1,4-二基))二吗啉(MPDB2),并将其与相变材料结合,制备了高灵敏度比率荧光温度计.由于化合物的高黏度响应性质,其在相变材料中的温度荧光响应范围低于体系熔点,因此得到在量程范围内为纯固体的相变材料荧光温度计,具有良好的加工性.作为黏度探针,一取代的MPDB1的荧光响应范围为100~3000 mPa·s,灵敏度高;而二取代的MPDB2则在100~46000 mPa·s的黏度区域有荧光响应,覆盖范围广.作为温度探针,MPDB1-聚乙二醇20000(PEG20000)体系的荧光温度响应区间为-10~50℃,最大相对灵敏度(Sr)为3.5%(10℃),绝对灵敏度(Sa)为4.6%(30℃),灵敏度较高,且其温度测量范围可以通过取代基数目和选用不同熔点的聚乙二醇介质调整,具有较强的适用性.

A near-infrared phosphorescent probe for F^- based on a cationic iridium(Ⅲ) complex with triarylboron moieties

In this work, a near-infrared (NIR) phosphorescent probe for F- based on a cationic Ir(III) complex [Ir(Bpq)2(quqo)]PF6 (1) with dimesitylboryl (Mes2B) groups on the cyclometalated CAN ligands (Bpq) and 2-(quinolin-2-yl)quinoxaline (quqo) as NAN ligand was designed and synthesized. The excited state properties of 1 were investigated in detail using molecular orbital calculations and experimental methods. Upon excitation, complex 1 shows NIR phosphorescent emission around 680 nm. Interestingly, the complex can be excited with long wavelength around 610 nm. Such long-wavelength excitation can reduce the background emission interference and improve the signal-to-noise ratio. Furthermore, the selective binding between boron atom and F- can give rise to the quenching of emission and realize the near-infrared phosphorescent sensing for F-. We wish that the results reported herein will be helpful for the further design of excellent near-infrared phosphorescent probes based on heavy-metal complexes.

A class of fascinating optoelectronic materials: Triarylboron compounds

Triarylboron compounds are significant optoelectronic materials due to their excellent emissive and electron-transport properties,and could be applied in organic light-emitting diodes as emissive and/or electron-transport layers.Triarylboron compounds have vacant pπ orbital and have received increasing interest as fluoride ion and cyanide ion sensors utilizing specific Lewis acid-base interaction.This review summarizes their structural characteristics,optical properties and applications in chemosensors for anions and optoelectronic devices developed in recent years and discusses the problems and prospects.

一种三芳基硼席夫碱比率荧光银离子探针的合成与性质

Ag^(+)可以杀菌消毒,促进伤口愈合,在日常用品以及医药等方面有重要作用,同时Ag^(+)也对人体蛋白质具有毒性。所以,建立快速高效的Ag^(+)检测方法具有非常重要的意义。我们设计合成了一种荧光三芳基硼席夫碱化合物NMBA,这种化合物可以在含水环境中与Ag^(+)结合,其共轭结构发生改变,从而使发光光谱在533 nm处出现新的强发光峰,而原有的460 nm处的发光峰强度不发生改变。用550 nm和450 nm两个波长处的荧光强度比率和体系中Ag^(+)浓度作图,具备良好的线性关系。化合物发光颜色也随着Ag^(+)浓度的增加,由蓝色逐渐变成黄绿色,便于裸眼观察和普通照相机拍摄。同时,化合物NMBA发光对其它常见金属离子没有响应,对Ag^(+)有良好的选择性。