Title:	Proton-Coupled Electron Transfer in the Aqueous Nanochannels of Lyotropic Liquid Crystals: Interplay of H-Bonding and Polarity Effects
Authors:	Das, Konoya Sappati, Subrahmanyam Bisht, Girish Singh Hazra, Partha
Keywords:	Reaction mechanisms Molecules Solvents Polarity Noncovalent interactions
Issue Date:	Mar-2021
Publisher:	American Chemical Society
Citation:	Journal of Physical Chemistry Letters, 2021, Vol. 12, p2651-2659
Abstract:	A molecular-level description of the aqueous nanochannels in lyotropic liquid crystals (LLCs) is crucial for their widespread utilization in diverse fields. Herein, the polarity and hydrogen bonding effects of LLC water molecules have been simultaneously explored using a single probe, 4′-N,N-dimethylamino-3-hydroxyflavone (DMA3HF), by the unique multiparametric sensitivity of the excited state proton-coupled electron transfer (PCET) phenomenon. The decreased ESIPT efficiency and the significantly retarded ESIPT dynamics (>20 times) of DMA3HF in the LLC phases suggests the dominant influence of strong hydrogen-bonded solute–solvent complexes that leads to a high activation barrier for ESIPT in the mesophases. The effects of hydrogen bonding on ESIPT have been elucidated by enhanced sampling techniques based on classical MD simulations of DMA3HF in explicit water. ESIPT via an extended hydrogen-bonded water wire is associated with a significantly high ESIPT activation barrier, substantiating the experimentally observed slow ESIPT dynamics inside the LLCs.
Description:	Restricted Access.
URI:	http://hdl.handle.net/2289/7772
ISSN:	1948-7185
Alternative Location:	https://doi.org/10.1021/acs.jpclett.1c00207
Copyright:	2021 American Chemical Society
Appears in Collections:	Research Papers (SCM)

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