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吡唑修饰的四苯基乙烯的AIE和力致荧光变色性质研究
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Abstract:
聚集诱导发光(AIE)分子由于在聚集态下具有优异的发光性能，同时其扭曲分子构象易形成疏松堆积，因此常被用于构筑机械力致荧光变色(MFC)材料。本文以四苯乙烯(TPE)为核心骨架，引入1-(四氢-2H-吡喃-2-基)-1H-吡唑单元，设计合成了一种新型吡唑修饰的TPE衍生物TPE-PY，并系统研究了其聚集诱导发光和力致荧光变色性能。结果表明，TPE-PY在THF/H？O混合溶剂中表现出显著的AIE特性：在纯THF溶液中几乎不发光，而随着水分数增加，分子逐渐形成纳米聚集体，荧光显著增强；当含水量达到90%时，其荧光强度达到纯THF溶液中的124倍，发射峰位于505 nm。TPE-PY初始固态粉末的荧光量子产率为0.604，AIE因子大于604，表明该分子具有优异的聚集态发光能力。进一步研究发现，TPE-PY具有高对比度、可逆的MFC性能。初始粉末在365 nm紫外光照射下发出蓝色荧光，最大发射峰位于467 nm；经机械研磨后，荧光颜色转变为黄绿色，发射峰红移至513 nm，红移幅度达46 nm，研磨态量子产率为0.558。经二氯甲烷蒸气熏蒸30 s后，其荧光颜色与发射光谱可恢复至初始状态，并在多次“研磨–熏蒸”循环中保持良好的可逆性与稳定性。PXRD结果表明，该力致荧光变色行为来源于机械刺激诱导的晶态–无定形态可逆相转变。荧光寿命和固态紫外吸收光谱分析进一步说明，研磨后发射红移与分子构象平面化、π共轭长度延长、π-π相互作用增强以及激子耦合增强有关。此外，基于TPE-PY优异的可逆MFC行为，本文还构建了可擦写无墨信息存储纸张，实现了信息的书写、擦除与重复使用。该研究为开发基于TPE单元的高对比度、可逆型力响应发光材料提供了新的分子设计思路。
Aggregation-induced emission (AIE) luminogens have attracted extensive attention in the field of smart luminescent materials because their twisted molecular conformations not only endow them with strong solid-state emission, but also favor loose molecular packing that is sensitive to external mechanical stimuli. In this work, a new pyrazole-functionalized tetraphenylethylene derivative, TPE-PY, was designed and synthesized by introducing 1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole units onto a tetraphenylethylene (TPE) core. Its aggregation-induced emission and mechanofluorochromic (MFC) properties were systematically investigated. The results show that TPE-PY exhibits pronounced AIE behavior in THF/H？O mixed solvents. It is almost non-emissive in pure THF, whereas its fluorescence is significantly enhanced as the water fraction increases and molecular nanoaggregates are formed. At a water fraction of 90%, the emission intensity reaches 124 times that in pure THF, with a maximum emission peak at 505 nm. The fluorescence quantum yield of the as-prepared solid is 0.604, and the AIE factor is greater than 604, indicating excellent aggregate-state emissive performance. TPE-PY also displays highly contrasted and reversible mechanofluorochromic behavior. The as-prepared powder emits bright blue fluorescence with an emission maximum at 467 nm under UV irradiation, while mechanical grinding converts the emission color to yellow-green and shifts the emission peak to 513 nm, corresponding to a red shift of 46 nm. The quantum yield of the ground sample remains as high as 0.558.
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