This work demonstrates the colorimetric and ratiometric fluorogenic detection of harmful organic peroxides (OPs) by using the S–S annulated perylene monoimide (PMISS) mediated emergence of a unique solid-state red-emitting perylene monoimide (PMI) derivative. PMISS dye has been successfully used for the detection of hazardous and toxic peroxides present in THF and 1,4-dioxane solvents via exhibiting a drastic visible color change from blue to red accompanied by a turn-on fluorescence response, thus offering a much-needed method to detect the presence of high-risk OPs. The chemical reaction between PMISS and peroxide present in THF yielded us two new PMISSO and PMISSO₂ derivatives, which were purified, and their structural and optical properties were subsequently investigated using ¹H-NMR, UV-vis absorption, and fluorescence spectroscopy, single-crystal X-ray diffraction analysis (PMISSO₂ only), and calorimetry. Among both species, PMISSO₂ exhibits unique fluorescence behavior in solution and, more notably, in the solid-state, while PMISSO displayed weak fluorescence in solution and inactivity in the solid-state. Single crystal X-ray analysis of PMISSO₂ shows that steric congestion is caused by the molecular motion of one bulky phenoxy-alkyl substituent in the bay position, and this leads to considerable twisting of the PMI π-scaffold supported by C–H⋯O hydrogen bonds between the SO₂ moieties and the 1,6-bay substituents. This type of molecular flexibility, as observed in the bay-substituent, sterically prohibits PMI aggregation in the solid-state, which gives rise to defined vibronic progressions in the solid-state absorption spectra and also enables it to emit bright red fluorescence. Time dependent density functional theory (TD-DFT) calculations obtained for PMISSO₂ of the crystal geometry nicely support the experimental observations made in both bulk and solution states. This outcome has added a novel dimension to studies of fundamental structure–property relationships of relevance in PMI-based organic electronics.

中文翻译：

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了解通过检测有害有机过氧化物实现的固态发射PMI的分子起源

这项工作证明了通过使用S-S环化per单酰亚胺（PMISS）介导的独特固态发红光per单酰亚胺（PMI）衍生物的出现，对有害有机过氧化物（OPs）进行了比色和比例荧光检测。PMISS染料通过显示出从蓝色到红色的剧烈可见颜色变化以及伴随的开启荧光响应，已成功地用于检测THF和1,4-二恶烷溶剂中存在的有害和有毒过氧化物，从而提供了急需的检测高风险OP的方法。PMISS和THF中存在的过氧化物之间的化学反应产生了两种新的PMISSO和PMISSO ₂衍生物，这些衍生物经过纯化，随后通过结构化学和光学性质进行了研究。¹ H-NMR，UV-vis吸收和荧光光谱，单晶X射线衍射分析（仅PMISSO ₂）和量热法。在这两个物种中，PMISSO ₂在溶液中表现出独特的荧光行为，尤其是在固态中，而PMISSO在溶液中表现出微弱的荧光，而在固态中则没有活性。对PMISSO _2的单晶X射线分析表明，空间拥塞是由一个大的苯氧基烷基取代基在托架位置的分子运动引起的，这导致C–H⋯O支撑的PMIπ支架发生相当大的扭曲。 SO ₂之间的氢键部分和1，6-bay取代基。如在海湾取代基中观察到的那样，这种类型的分子柔性在空间上阻止了固态的PMI聚集，这在固态吸收光谱中产生了确定的电子振动，并且还使其能够发出明亮的红色荧光。对于晶体几何结构的PMISSO ₂获得的时间依赖性密度泛函理论（TD-DFT）计算很好地支持了在体态和溶液态下的实验观察。这一结果为基于PMI的有机电子学中相关的基本结构与属性关系的研究增加了新的维度。