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Amino proton donors in excited-state intramolecular proton-transfer reactions
Nature Reviews Chemistry ( IF 38.1 ) Pub Date : 2018-07-03 , DOI: 10.1038/s41570-018-0020-z
Chi-Lin Chen , Yi-Ting Chen , Alexander P. Demchenko , Pi-Tai Chou

Proton transfer involving site-specific hydrogen-bonding interactions is one of the most fundamental and important reactions in chemistry and biology. Deliberately triggering this reaction by photoexcitation enables unique and insightful mechanistic analyses. This Review describes a particularly effective method that involves exciting a photoacid containing both an amine and a basic residue and monitoring the ensuing excited-state intramolecular proton-transfer (ESIPT) reactions. Replacing a H atom on the amine with another substituent R modulates the acidity of the amine and allows for the excited-state hydrogen-bond strength to be tuned over a very broad range. In this way, one can draw empirical correlations between N−H bond distances, acidity, hydrogen-bond strength and the ESIPT kinetics and thermodynamics. For example, stronger intramolecular N−H···N hydrogen bonding leads to faster and more exergonic ESIPT. Tuning the amine and basic residues allows one to switch the ESIPT mechanism between the kinetic and thermodynamic regimes, such that molecules can generate ratiometric emission, which is suitable for white-light generation and two-colour imaging. The identity of the amine substituent R not only affects the acidity but can be differentially sensitive towards the local chemical environment. Thus, the R group transduces environmental changes into modified ESIPT rates and/or mechanisms. Such studies open new frontiers in the fundamental aspects of proton transfer in amines, as well as their largely unexplored potential applications.



中文翻译:

激发态分子内质子转移反应中的氨基质子供体

涉及特定位置的氢键相互作用的质子转移是化学和生物学中最基本,最重要的反应之一。通过光激发故意触发此反应,可以进行独特而深刻的机械分析。这篇综述描述了一种特别有效的方法,该方法涉及激发同时包含胺和碱性残基的光酸,并监测随后的激发态分子内质子转移(ESIPT)反应。用另一个取代基R取代胺上的H原子可调节胺的酸度,并允许在很宽的范围内调节激发态氢键强度。以此方式,可以得出NH键距离,酸度,氢键强度与ESIPT动力学和热力学之间的经验相关性。例如,分子内NH···N氢键越强,ESIPT的作用就越快。调节胺和碱性残基可使人们在动力学和热力学范围之间切换ESIPT机制,从而使分子可以产生比例发射,适用于白光产生和双色成像。胺取代基R的身份不仅影响酸度,而且对局部化学环境可能具有不同的敏感性。因此,R基团将环境变化转化为改良的ESIPT速率和/或机制。这些研究为胺中质子转移的基本方面及其在很大程度上未开发的潜在应用方面开辟了新的领域。调节胺和碱性残基可使人们在动力学和热力学范围之间切换ESIPT机制,从而使分子可以产生比例发射,适用于白光产生和双色成像。胺取代基R的身份不仅影响酸度,而且对局部化学环境可能具有不同的敏感性。因此,R基团将环境变化转化为改良的ESIPT速率和/或机制。这些研究为胺中质子转移的基本方面及其在很大程度上未开发的潜在应用方面开辟了新的领域。调节胺和碱性残基可使人们在动力学和热力学范围之间切换ESIPT机制,从而使分子可以产生比例发射,适用于白光产生和双色成像。胺取代基R的身份不仅影响酸度,而且对局部化学环境可能具有不同的敏感性。因此,R基团将环境变化转化为改良的ESIPT速率和/或机制。这些研究为胺中质子转移的基本方面及其在很大程度上未开发的潜在应用方面开辟了新的领域。胺取代基R的身份不仅影响酸度,而且对局部化学环境可能具有不同的敏感性。因此,R基团将环境变化转化为改良的ESIPT速率和/或机制。这些研究为胺中质子转移的基本方面及其在很大程度上未开发的潜在应用方面开辟了新的领域。胺取代基R的身份不仅影响酸度,而且对局部化学环境可能具有不同的敏感性。因此,R基团将环境变化转化为改良的ESIPT速率和/或机制。这些研究为胺中质子转移的基本方面及其在很大程度上未开发的潜在应用方面开辟了新的领域。

更新日期:2018-07-04
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