Femtosecond Pump–Probe Spectroscopy of Photoinduced Tautomerism

Lochbrunner, Stefan

doi:10.1002/9783527658824.ch4

Cited by 1 publication

(1 citation statement)

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“…For example, the C 2 vO a , O a ⋯H 1 , H the formation of a relatively stronger IMHB in water as compared to that in vacuo. [64][65][66][67] Such changes in the optimized geometry parameters are found to be in consensus with the modulations in the electronic charge density distribution (according to the Mulliken scheme) over the atoms as compiled in Table 7. 67 Further, in order to envisage the probable influence of microsolvation on the probe molecule, the geometry of a 1 : 1 molecular cluster with water (Scheme 3) has been optimized in the SCRF of water.…”

Section: Computational Results In Solvent Reaction Fieldsupporting

confidence: 67%

A critical approach toward resonance-assistance in the intramolecular hydrogen bond interaction of 3,5-diiodosalicylic acid: a spectroscopic and computational investigation

Paul

Ghosh

Mondal

et al. 2015

Photochem Photobiol Sci

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The photophysics of a prospective drug molecule, 3,5-diiodosalicylic acid (3,5-DISA), having a wide spectrum of biological and medicinal applications, have been investigated using spectroscopic techniques and computational analyses. The remarkably large Stokes' shifts in various solvents from 3,5-DISA has been intertwined with the occurrence of an excited-state intramolecular proton transfer (ESIPT) reaction. Concurrently, the emergence of an intriguing dual emission feature in less interacting solvents is also reported and the spectral response of 3,5-DISA toward the variation of medium acidity/basicity has been exploited to decipher the nature of various species present in different solvents. Our experimental results, unveiling the occurrence of an ESIPT reaction in 3,5-DISA, have been aptly substantiated from computational studies in which the operation of ESIPT has been explored from structural as well as energetics (analysis of potential energy surface (PES)) perspectives. A major focus of the present study is on the evaluation of the intramolecular hydrogen bond (IMHB) interaction in 3,5-DISA, including the application of various methodologies to estimate the IMHB energy and subsequently, an in-depth analysis of the IMHB interaction reveals its partially covalent nature through the application of advanced quantum chemical tools, e.g., the natural bond orbital (NBO) method. In this context, the interplay between the aromaticity of the benzene nucleus and the IMHB energy has been rigorously explored, showing indications for the occurrence of resonance-assisted hydrogen bonding (RAHB) in 3,5-DISA. To this end, the geometric as well as magnetic criteria of aromaticity have been analyzed.

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