酸致变色二硝基苯-肼基衍生物的光行为:一个完全内转化的例子

Photochem Pub Date : 2022-10-10 DOI:10.3390/photochem2040054
L. Mencaroni, A. Cesaretti, G. Consiglio, F. Elisei, C. Fortuna, A. Spalletti
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引用次数: 0

摘要

光化学研究一直在寻找新的化合物,这些化合物可以在从医学到环境科学的各种应用中发挥作用。从这个意义上说,具有质子基团的推挽化合物代表了一类有趣的分子,因为它们可以被证明对介质的酸度和极性的变化都很敏感,成为有价值的传感器和探针。因此,本文专门设计并合成了一种具有多个质子中心的二硝基苯基酰肼衍生物。该分子在可见光下表现出重要的酸致变色,在酸性、中性和碱性条件下具有三种不同的质子化物种,每种都具有特殊的吸收光谱。该化合物的光物理特性揭示了飞秒瞬态吸收实验所描述的超快激发态失活,以及观察到的溶剂变色和量子力学计算所支持的电荷转移动力学的暗示。这些性质导致了几乎无法检测到的荧光,加上可忽略不计的系统间交叉和缺乏反应途径,表明了对完全非辐射失活机制的偏好,即内部转换。这种有趣的行为激发了人们对所研究的酸致变色染料作为光声成像探针的可能应用的兴趣,这为经典荧光成像提供了一种替代方案。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Photobehavior of an Acidochromic Dinitrophenyl-Hydrazinylidene Derivative: A Case of Total Internal Conversion
Research in photochemistry is always looking for novel compounds that can serve a role in applications ranging from medicine to environmental science. Push–pull compounds with protonable groups represent an interesting class of molecules in this sense, as they can prove to be sensitive to changes in both the acidity and polarity of the medium, becoming valuable as sensors and probes. Hence, in this work, a new dinitrophenyl-hydrazinylidene derivative with multiple protonable centers has been specifically designed and synthesized. The molecule showed an important acidochromism in the visible, with three differently-protonated species under acidic, neutral, and basic conditions, each characterized by a peculiar absorption spectrum. The photophysical characterization of this compound revealed an ultrafast excited-state deactivation, as described by femtosecond transient absorption experiments, and the hints of charge-transfer dynamics, as supported by the observed solvatochromism and quantum-mechanical calculations. These properties led to almost undetectable fluorescence that, together with negligible intersystem crossing and the absence of reactive pathways, points to the preference for a total non-radiative deactivation mechanism, i.e., internal conversion. This intriguing behavior stimulates interest in light of possible applications of the investigated acidochromic dye as a probe in photoacoustic imaging, which offers an alternative to classical fluorescence imaging.
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CiteScore
3.60
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