2-位取代的三苯胺—蒽衍生物的合成与压致变色性能  

Synthesis and Piezofluorochromic Properties of a 2-Substituted Triphenylamine-Anthracene Derivative

作　　者：谢焕然 崔浩 阎东 李辉 梁作芹[1] 王筱梅[1] 叶常青[1] XIE Huan-ran;CUI Hao;YAN Dong;LI Hui;LIANG Zuo-qin;WANG Xiao-mei;YE Chang-qing(School of Materials Science and Engineering,Suzhou University of Science and Technology,Suzhou 215009,China)

机构地区：[1]苏州科技大学材料科学与工程学院,江苏苏州215009

出　　处：《光谱学与光谱分析》2023年第6期1776-1780,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(51803147);江苏省环境功能材料重点实验室开放课题(SJHG1803)资助。

摘　　要：有机压致变色材料是一种在外界压力刺激下,自身发光性能发生变化的智能材料,在压敏元件、信息存储显示、压致传感等领域具有广阔的应用前景。具有螺旋桨结构的三苯胺能够抑制分子间强的相互作用和紧密堆积,在压致变色领域越来越受到关注。以2-甲基蒽醌为原料,经锌粉还原、溴素溴化和钯催化的Suzuki偶联反应合成了一个以三苯胺为支、蒽-2-甲基为核的新型化合物9,10-二[4-(N,N′-二苯基氨基)苯基]-2-甲基蒽(TPA-MA),其结构经~1H NMR,^(13)C NMR和MS表征,采用紫外-可见吸收光谱、荧光光谱、 X射线衍射光谱和密度泛函理论计算等研究了其溶剂效应和压致变色性能。随着溶剂极性的增加,TPA-MA的紫外-可见吸收光谱几乎保持不变,而荧光光谱峰位逐渐红移,并且荧光强度呈现降低趋势。Lippert-Mataga曲线和理论计算结果表明TPA-MA明显的溶剂效应是分子内电荷转移特性引起的。同时,TPA-MA具有典型的压致变色性能。在固态时其发射峰位于450 nm,呈现比较强的蓝色荧光。研磨后,发射峰红移至466 nm,并伴随荧光强度的降低。研磨后的粉末置于二氯甲烷蒸汽中或加热至150℃,又能恢复至原来的蓝色荧光,具有循环反复性。X射线衍射光谱表明TPA-MA的压致变色性能是晶体结构变化引起。综合实验和文献报道,蒽2-位甲基基团的引入可能进一步增大了TPA-MA分子扭曲构象,抑制分子间相互作用,使得晶体结构堆积更加疏松。当外力作用时,晶体结构容易被破坏,分子结构趋于平面化,增强分子内电荷转移特性,导致TPA-MA发射峰红移并呈现荧光猝灭现象。Piezofluorochromic organic materials are a class of smart materials with fluorescent change in response to external force stimuli,which have broad application prospects in pressure-sensitive devices,optical information storage and mechanosensory.Triphenylamine with a propeller structure can inhibit strong intermolecular interaction and close packing,which has attracted much attention in piezofluorochromism.A new compound 9,10-Bis[4-(N,N′-diphenylamino)phenyl]-2-methylanthracene(TPA-MA)with triphenylamine as branch and anthracene-2-methyl as core was prepared from^(2)-methylanthraquinone by zinc powder reduction,bromination with bromineand palladium catalyzed Suzuki coupling reaction,and characterized by 1H NMR,13 C NMR and MS.The solvatochromism effect and piezofluorochromic properties were studied by UV-Vis,photoluminescence(PL),X-ray diffraction(XRD)spectra,and density functional theory calculation.With the increase of solvent polarity,the absorption spectra of TPA-MA remain almost unchanged,but the PL peak is progressively red-shifted,accompanied by the decrease of PL intensity.The Lippert-Mataga plots and the density functional theory calculations reveal that the intramolecular charge transfer(ICT)characteristic of TPA-MA is responsible for the large solvatochromism effect.Meanwhile,TPA-MA has typical piezofluorochromic properties.In the solid state,the PL peak of TPA-MA is at 450 nm with strong blue fluorescence.Upon grinding,the PL peak is red-shifted to 466 nm,accompanied by a decrease in PL intensity.When the ground powder is exposed to dichloromethane vapor or heated to 150℃,it can return to the original blue fluorescence and has repeatability.XRD spectra show that the piezofluorochromic properties of TPA-MA are caused by the change of crystal packing arrangement.The experiments and reported literature indicate that introducing an anthracene 2-methyl group can further cause a molecular twist in the luminophore skeleton to inhibit the intermolecular interaction and make the crystal packing looser.When

关 键 词：三苯胺 偶联反应 溶剂效应 压致变色 

分 类 号：O657.3[理学—分析化学]