Structurally simple thienodipyrandione-containing reversible fluorescent switching piezo- and acido-chromic materials
Structurally simple thienodipyrandione-containing reversible fluorescent switching piezo- and acido-chromic materials
复制标题
DOI：
10.1039/c3tc31504e
复制
发表时间：
2013-01-01
影响因子：
6.4
通讯作者：
Sun, Shih-Sheng
中科院分区：
文献类型：
--
作者：
Rao, Rajeswara M.;Liao, Chia-Wei;Sun, Shih-Sheng
我们在这里报告的结构-性能的相关性的一系列蒽/芘衍生物接枝在一个刚性的，平面的，以及共轭的内环烯基内酯（噻吩并二吡喃二酮），表现出聚集诱导的排放。与典型的基于亚乙烯基的固态荧光材料不同，刚性噻吩并二吡喃二酮部分可以赋予更高阶的构象扭曲以及由于羰基的存在而通过C-H中心点O相互作用增强的分子间相互作用，这导致增强的热稳定性。化合物TDAn和TDAnPh表现出不同的压致荧光变色特性，其中发射颜色可以通过研磨和加热来切换。基于各种光谱技术，包括XRD，DSC和NMR，所观察到的压致变色发射归因于从结构结晶（有序）到非晶（无序）状态或反之亦然的相变的结果。最独特的是，其中一种蒽衍生物TDAn显示出特定的酸荧光显色性，而另一种同系物TDAnPh则没有，尽管它们在结构上非常相似。晶体结构分析表明，C-H中心点、中心点、中心点O、π-π和C-H中心点、中心点、中心点π等多种次级相互作用的组合在超分子组装体中发挥了关键作用，从而显示出这种独特的功能。目前的研究揭示了一类新的刺激响应材料，在微环境传感，光开关和记录的应用具有巨大的潜力。
We report here the structure-property correlations of a series of anthracene/pyrene derivatives grafted on a rigid, planar, and well conjugated endo-cyclic alkenyl lactone (thienodipyrandione) that exhibited aggregation induced emission. Unlike typical vinylene based solid-state fluorescence materials, rigid thienodipyrandione moieties can bestow a higher order of conformational twist as well as enhanced intermolecular interactions by C-H center dot center dot center dot O interactions due to the presence of a carbonyl group that leads to enhanced thermal stability. Compounds TDAn and TDAnPh exhibit distinct piezofluorochromic properties in which emission colors can be switched by grinding and heating. Based on a variety of spectroscopic techniques including XRD, DSC, and NMR, the observed piezochromic emission is attributed to the result of phase transition from structural crystalline (order) to amorphous (disorder) state or vice versa. Most uniquely, one of the anthracene derivatives, TDAn, displayed specific acido-fluorochromism whereas the other congener, TDAnPh, did not, even though they are structurally very similar. Crystal structure analysis revealed that a combination of various secondary interactions such as C-H center dot center dot center dot O, pi-pi and C-H center dot center dot center dot pi interactions all play key roles in the supramolecular assemblies to display such distinctive features. The current study has disclosed a class of new stimuli-responsive materials with great potential in applications for micro-environmental sensing, optical switching and recording.