A supramolecular approach towards the photorelease of encapsulated caged acids in water: 7-diethylaminothio-4-coumarinyl molecules as triggers.

Abstract

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.