Sujit Kumar Ghosh, Shreya Chatterjee, Paras Pratim Boruah, Satyajit Mandal, José P Da Silva, Varadharajan Srinivasan, Vaidhyanathan Ramamurthy
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The thiocarbonyl chromophore extends the absorption of coumarinyl trigger to visible range while enhancing the intersystem crossing (ISC) to the triplet state, making it the reactive state. Despite the non-polar environment within the OA capsules the photocleavage occurs in a heterolytic fashion to release the conjugate base and the used trigger as triplet carbocation in an adiabatic process. Interestingly, the triplet carbocation crosses to the ground singlet surface (closed shell singlet carbocation) with the help of water molecules, possibly aided by C = S chromophore. Utilizing the known excited state dynamics of related thiocoumarinyl and coumarinyl systems, we have identified a few of the important mechanistic features of the photorelease process of 7-diethylaminothio-4-coumarinyl derivatives. Ultrafast excited state dynamic studies and quantum chemical calculations planned should help us better understand the photorelease process so as to effectively exploit the proposed system for potential applications.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":" ","pages":"2057-2073"},"PeriodicalIF":2.7000,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A supramolecular approach towards the photorelease of encapsulated caged acids in water: 7-diethylaminothio-4-coumarinyl molecules as triggers.\",\"authors\":\"Sujit Kumar Ghosh, Shreya Chatterjee, Paras Pratim Boruah, Satyajit Mandal, José P Da Silva, Varadharajan Srinivasan, Vaidhyanathan Ramamurthy\",\"doi\":\"10.1007/s43630-024-00651-1\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Herein, we establish the release of aliphatic acids in water upon excitation of 7-diethylaminothio-4-coumarinyl derivatives encapsulated within the organic host octa acid (OA). 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Interestingly, the triplet carbocation crosses to the ground singlet surface (closed shell singlet carbocation) with the help of water molecules, possibly aided by C = S chromophore. Utilizing the known excited state dynamics of related thiocoumarinyl and coumarinyl systems, we have identified a few of the important mechanistic features of the photorelease process of 7-diethylaminothio-4-coumarinyl derivatives. 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引用次数: 0
摘要
在这里,我们确定了当被封装在有机宿主辛酸(OA)中的 7-二乙基硫代氨基-4-香豆素基衍生物受到激发时,脂肪族酸会在水中释放出来。这里使用的 7-二乙基硫代氨基-4-香豆素基骨架作为触发器,可从激发的三重态光释放笼状分子,这与其羰基类似物形成鲜明对比,后者已知会从激发的单重态发生相同的反应。封装在 OA 中的分子可以溶解在水中,否则就不能溶于水,而且在脂肪族酸释放后,还能将所用的触发器保留在自身中。这种超分子特性为光释方法带来了新的特点。硫代羰基发色团将香豆酰触发器的吸收范围扩大到可见光范围,同时增强了三重态的系统间交叉(ISC),使其成为反应态。尽管 OA 胶囊内存在非极性环境,但光裂解仍以异性分解的方式进行,在绝热过程中释放出共轭碱和作为三重碳位的触发剂。有趣的是,三重碳位在水分子的帮助下,可能在 C = S 发色团的帮助下,穿过地面单质表面(闭壳单质碳位)。利用相关硫代香豆素基和香豆素基系统的已知激发态动力学,我们确定了 7-二乙基硫代氨基-4-香豆素基衍生物光释放过程的一些重要机理特征。计划进行的超快激发态动态研究和量子化学计算应有助于我们更好地理解光释放过程,从而有效地利用拟议系统的潜在应用。
A supramolecular approach towards the photorelease of encapsulated caged acids in water: 7-diethylaminothio-4-coumarinyl molecules as triggers.
Herein, we establish the release of aliphatic acids in water upon excitation of 7-diethylaminothio-4-coumarinyl derivatives encapsulated within the organic host octa acid (OA). The 7-diethylaminothio-4-coumarinyl skeleton, employed here as the trigger, photoreleases caged molecules from the excited triplet state, in contrast to its carbonyl analogue, where the same reaction is known to occur from the excited singlet state. Encapsulation in OA solubilizes molecules in water that are otherwise water-insoluble, and retains the used trigger within itself following the release of the aliphatic acid. Such supramolecular characteristics usher in new features to the photorelease methodology. The thiocarbonyl chromophore extends the absorption of coumarinyl trigger to visible range while enhancing the intersystem crossing (ISC) to the triplet state, making it the reactive state. Despite the non-polar environment within the OA capsules the photocleavage occurs in a heterolytic fashion to release the conjugate base and the used trigger as triplet carbocation in an adiabatic process. Interestingly, the triplet carbocation crosses to the ground singlet surface (closed shell singlet carbocation) with the help of water molecules, possibly aided by C = S chromophore. Utilizing the known excited state dynamics of related thiocoumarinyl and coumarinyl systems, we have identified a few of the important mechanistic features of the photorelease process of 7-diethylaminothio-4-coumarinyl derivatives. Ultrafast excited state dynamic studies and quantum chemical calculations planned should help us better understand the photorelease process so as to effectively exploit the proposed system for potential applications.