Unique twisted donor–acceptor cruciform π-architectures exhibiting aggregation-induced emission and stimuli-response behaviors
Unique twisted donor–acceptor cruciform π-architectures exhibiting aggregation-induced emission and stimuli-response behaviors
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独特的扭曲供体-受体十字形结构表现出聚集诱导的发射和刺激响应行为
DOI：
10.1016/j.dyepig.2019.04.015
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发表时间：
2019-08
影响因子：
4.5
通讯作者：
Chao Zhang
中科院分区：
文献类型：
--
作者：
Yonghui Wang;Jingran Liu;Weiliang Yuan;Ying Wang;Hongke Zhou;Xingliang Liu;Jianfang Cao;Chao Zhang
设计并成功地制备了两个扭曲的π共轭十字形发光体MDCS-TPA和FMDCS-TPA，其中两个共轭给受体基团相交于中心苯核。理论计算和光谱分析表明，这两个化合物具有独特的分子内电荷转移(ICT)过程，分别来自富电子的三苯胺和贫电子的氰基苯乙基单元。在固态下，MDCS-TPA和FMDCS-TPA表现出AIE效应，荧光量子产率分别为0.321和0.312。有趣的是，MDCS-TPA和FMDCS-TPA具有明显的机械荧光(MFC)行为。两种发光体的粉末均能发出较强的绿色荧光(491 nm)和黄绿色荧光(529 nm)，研磨后荧光颜色分别变为黄色(542 nm)和橙色(576 nm)，红移分别为51 nm和47 nm。通过重复研磨-烟化和研磨-退火过程，这种机械变色是可逆的。MDCS-TPA和FMDCS-TPA的MFC行为源于晶态和非晶态之间的转变，研磨引起的红移是分子构象的平坦化和随后在外力刺激下的平面分子内电荷转移(PICT)的结果。
Two twisted π-conjugated cruciform luminophoresMDCS-TPAandFMDCS-TPAcontaining two conjugated donor and acceptor groups intersecting at the central benzene core have been rationally designed and successfully prepared. The two compounds display unique intramolecular charge-transfer (ICT) process from electron-rich triphenylamine and electron-poor cyanostyryl units, which are evidenced by theoretical calculations and spectral analysis.MDCS-TPAandFMDCS-TPAexhibit AIE effects with high fluorescence quantum yields of 0.321 and 0.312 in the solid state. Interestingly,MDCS-TPAandFMDCS-TPApossess the distinct mechanofluorochromic (MFC) behavior. The as-prepared powders of the two luminophores could emit strong green (491 nm) and yellow-green fluorescence (529 nm), and the fluorescence color changed into yellow (542 nm) and orange (576 nm) after grinding, respectively, giving the red shifts of 51 nm and 47 nm. Such mechanochromism is reversible by repeating both the grinding-fuming and grinding-annealing processes. The MFC behavior ofMDCS-TPAandFMDCS-TPAoriginates from the transition between the crystalline and amorphous states and the red-shifts induced by grinding is the result of the planarization of the molecular conformation and subsequent planar intramolecular charge transfer (PICT) under the external force stimuli.
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