Modulation of the Excited State Intramolecular Electron Transfer Reaction and Dual Fluorescence of Crystal Violet Lactone in Room Temperature Ionic Liquids

Santhosh, Kotni; Samanta, Anunay

doi:10.1021/jp1039805

Cited by 52 publications

(45 citation statements)

References 51 publications

(114 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The results of our simulation studies that are presented in chapter 3 indicate that the electron transfer reaction kinetics is indeed local solvent environment dependent. Our simulation results are strongly supported by experiments and it appears that this phenomenon has now been observed to be relevant not only in fluorescence experiments but also in electron transfer reactions, proton transfer reactions and isomerization reactions [83,113,79,80].…”

supporting

confidence: 81%

“…local solvent environment dependent. Our results provide molecular level understanding of experiments in which the reaction kinetics is observed to be an absorption wavelength dependent [83,113,79,80,111]. Due to the time scale difference between the electron transfer process (fast) and the dynamics of the solvent (slow) by selective red-edge excitation one is able to influence the outcome of an electron transfer reaction.…”

Section: Resultsmentioning

confidence: 65%

“…One of the contributions of this thesis to our understanding of room temperature ionic liquids is that we show this phenomenon to be relevant not only to spectroscopic problems, but also to more general chemical problems such as electron transfer. Many experiments have since followed [83,113,79,80,111] confirming that indeed distributed dynamics is ubiquitous in these systems at room temperature. In particular, our studies have indicated that Marcus theory is likely valid for intra-molecular electron transfer reactions in room temperature ionic liquids but the shape of Marcus parabolas is local solvent environment dependent.…”

Section: Chapter 7 Summary Impact and Future Directionsmentioning

confidence: 95%

“…This chapter attempts to extend our understanding of distributed dynamics in ionic liquids beyond fluorescence and into the realm of chemical reactivity. It turns out that since we first published our work on absorption wavelength dependent electron transfer [4], this phenomenon has been demonstrated to be important in many different experiments in ionic liquids [83,113,79,80,111,21].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical studies on the structure and dynamics of room-temperature ionic liquids

Annapureddy¹

View full text Add to dashboard Cite

In this thesis, we present our studies on the structure and dynamics of novel Room-Temperature Ionic Liquids. Through our computer simulations we demonstrate that the kinetics of photo induced electron transfer reaction between S 1 and S 2 states of Crystal Violet Lactone in N-propyl-N-methylpyrrolidiniumbis(trifluoromethylsulfonyl)imide([Pr + 31 ][NTf 2 − ]) room temperature ionic liquid is local solvent environment dependent, because emission time scales are smaller than solvent relaxation time scales. This behavior is characteristic of ionic liquids but uncommon in conventional solvents. Therefore ionic liquids open a window of opportunity for manipulating the outcome of chemical reactions simply by tuning the initial excitation wavelength. We performed Molecular dynamics simulations of mixtures of 1-hexyl-3-methyl imidazoliumhexafluorophosphate ([C 6 MIM + ][PF − 6 ]) and water in order to investigate how small amounts of water affect the translational and rotational dynamics of ionic liquids. We find that water is closely associated with the anions and that its presence enhances both the translational and rotational dynamics of the ionic liquid. In agreement with experiments, we find that the fluorescence spectra of Coumarin-153 is red-shifted because of the presence of water. Small amounts of water enhance the speed of relaxation of the solvent surrounding the solute probe after photo-excitation, but only at a local environment level. Interconversion between environments still occurs on a long time scale compared with the fluorescence lifetime of the probe.To interpret the features of x-ray scattering structure factor of room temper-ature ionic liquids we introduce a set of general theoretical partitions of real and reciprocal space correlations that allow for unambiguous analysis of all intra-and inter-ionic contributions to the structure function and coherent scattering intensity.Through our simulations we could explain the origin of various peaks in the x-ray structure function of methyltributylammonium bis(trifluoromethylsulfonyl)amide.In order understand the origin of the first sharp diffraction peak in the x ray structure factor of Imidazolium based ionic liquids, we use several different computational techniques to thoroughly dissect the atomistic components giving rise to the low frequency first sharp diffraction peak as well as other features in the structure function (S(q)). By understanding how S(q) changes as Imidazolium based ionic systems undergo solid-liquid phase transition, and by artificially perturbing the liquid structure in a way that directly couples to the intensity of the first sharp diffraction peak, we are able to identify in a rigorous way its geometric origin. Abstract Approved: Thesis Supervisor To my beloved family ii ACKNOWLEDGMENTS I consider this to be an important section of my dissertation. I attempt sincerely to express my gratitude to all those who have contributed professionally and personally to make my grad school experience wonderful. First and foremost, I would like...

show abstract

supporting

confidence: 81%

Section: Resultsmentioning

confidence: 65%

Section: Chapter 7 Summary Impact and Future Directionsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Theoretical studies on the structure and dynamics of room-temperature ionic liquids

Annapureddy¹

View full text Add to dashboard Cite

show abstract

“…Several photophysical studies have been carried out in RTILs . Among all the popularly used fluorescent probes, the most prominently used probe is substituted amino coumarins.…”

Section: Introductionmentioning

confidence: 99%

Photophysics and Rotational Dynamics of a Hydrophilic Molecule in a Room Temperature Ionic Liquid

Chatterjee

Maity

Ahmed

et al. 2015

Photochem & Photobiology

View full text Add to dashboard Cite

We have studied the photophysics and rotational diffusion of hydrophilic solute 7-(N, N'-diethylamino)coumarin-3-carboxylic acid (7-DCCA) in a room temperature ionic liquid methyltrioctylammonium bis(trifluoromethylsulfonyl) imide ([N1888 ][NTf2 ]). Comparison of activation energies of viscous flow and nonradiative decay shows that the photophysical properties of 7-DCCA are not guided by the bulk viscosity of the medium but are dependent on the specific solute solvent interaction and structural heterogeneity of the medium. The rotational relaxation behaviour of 7-DCCA in [N1888 ][NTf2] shows significant deviation from the Stokes Einstein Debye hydrodynamic model of rotational diffusion. This is indicative of the influence of specific solute solvent interaction on the rotational relaxation behaviour of 7-DCCA. Comparison of activation energy of rotational relaxation with activation energy of viscous flow clearly reinforces our assumption that the structural heterogeneity of the medium and specific solute solvent interaction plays a dominant role on the rotational diffusion instead of bulk viscosity.

show abstract

Fluorescence Spectroscopy to Probe Ionic Liquid‐Based Systems

Pandey

Trivedi

Pandey³

2018

Encyclopedia of Analytical Chemistry

View full text Add to dashboard Cite

Owing to its inherent sensitivity coupled with multidimensionality, fluorescence spectroscopy has established itself as a versatile tool to investigate complex chemical systems in analytical chemistry. Ionic liquids, for the last couple of decades or so, have emerged as intriguing modern materials in science and technology that display an array of useful and sometimes unconventional features. Steady‐state fluorescence intensity and anisotropy and time‐resolved excited‐state emission intensity and anisotropy decays along with other advanced fluorescence techniques have been employed effectively to analyze, characterize, and explore ionic liquids and ionic liquid‐based systems. The extent of dipolarity afforded by ionic liquids as well as cosolvent/supercritical fluid‐added ionic liquid systems is readily manifested through the response of judiciously selected fluorescence polarity probes. Transient solvation measurements carried out by means of time‐resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process within ionic liquids. Dynamic Stokes' shift of appropriate fluorescence probes reveals the presence of several components, thus highlighting the complexity of solvation within ionic liquids and ionic liquid‐based media. Various fluorescence spectroscopic tools are used to establish and characterize macromolecular (surfactant and polymer) and dye aggregation within ionic liquids and ionic liquid‐based media along with aggregation of surface‐active ionic liquids (SAILs) in water.

show abstract

Modulation of the Excited State Intramolecular Electron Transfer Reaction and Dual Fluorescence of Crystal Violet Lactone in Room Temperature Ionic Liquids

Cited by 52 publications

References 51 publications

Theoretical studies on the structure and dynamics of room-temperature ionic liquids

Theoretical studies on the structure and dynamics of room-temperature ionic liquids

Photophysics and Rotational Dynamics of a Hydrophilic Molecule in a Room Temperature Ionic Liquid

Fluorescence Spectroscopy to Probe Ionic Liquid‐Based Systems

Contact Info

Product

Resources

About