Ultrafast Solvation Dynamics Reveal that Octa Acid Capsule's Interior Dryness Depends on the Guest

Aritra Das, Gaurav Sharma, Nareshbabu Kamatham, Rajeev Prabhakar, Pratik Sen, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticle

Abstract

Coumarins are well-known to exhibit environment-dependent excited-state behavior. We have exploited this feature to probe the accessibility of solvent water molecules to coumarins (guest) encapsulated within an organic capsule (host). Two sets of coumarins, one small that fits well within the capsule and the other larger that fits within an enlarged capsule, are used as guests. In our study, the two sets of coumarins serve different purposes: One is employed to explore electron transfer across the capsule and the other to release photoprotected acids into the aqueous environment. The capsule is made up of two molecules of octa acid (OA) and is soluble in an aqueous medium under slightly basic conditions. Molecular modeling studies revealed that while the OA capsule is fully closed with no access to water in the case of smaller coumarins, with the larger molecules, the capsule is not tight and the guest is in contact with water molecules, the number being dependent on the size of the coumarin. We have used the ultrafast time-dependent Stokes shift method to understand the solvent dynamics around the above guest molecules encapsulated within an OA capsule in an aqueous medium. Results depict that for the smaller sets of coumarins, water cannot access the guests within the OA cavity during their excited state lifetime. However, the case is completely different for the larger coumaryl esters. Distorted capsule structure exposes the guest to water, and a dynamics Stokes shift is observed. The average solvation time decreases with the increasing size of guests that clearly indicates accessibility of the encapsulated guests toward greater number of water molecules as the capsule structure distorts with increasing size of the guests. Results of the ultrafast solvation dynamics are consistent with that of molecular dynamics simulation.

Original languageEnglish (US)
Pages (from-to)5928-5936
Number of pages9
JournalJournal of Physical Chemistry A
Volume123
Issue number28
DOIs
StatePublished - Jun 19 2019
Externally publishedYes

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Solvation
capsules
Capsules
solvation
Coumarins
acids
Acids
Molecules
Water
water
molecules
Excited states
Molecular modeling
shift
excitation
Molecular dynamics
esters
electron transfer
Esters
molecular dynamics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ultrafast Solvation Dynamics Reveal that Octa Acid Capsule's Interior Dryness Depends on the Guest. / Das, Aritra; Sharma, Gaurav; Kamatham, Nareshbabu; Prabhakar, Rajeev; Sen, Pratik; Ramamurthy, Vaidhyanathan.

In: Journal of Physical Chemistry A, Vol. 123, No. 28, 19.06.2019, p. 5928-5936.

Research output: Contribution to journalArticle

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