Ultrafast Solvation Dynamics and Vibrational Coherences of Halogenated Boron-Dipyrromethene Derivatives Revealed through Two-Dimensional Electronic Spectroscopy

Lee, Yumin; Das, Saptaparna; Malamakal, Roy M.; Meloni, Stephen L.; Chenoweth, David M.; Anna, Jessica M.

doi:10.1021/jacs.7b08558

Cited by 35 publications

(55 citation statements)

References 108 publications

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“…The values found for the MeOH solutions are in reasonably good agreement with recent measurements on a molecule with a similar structure. 30 These time constants are very fast and, especially in the case of PHDB, close to the time resolution of the experiment, leading to a non-negligible uncertainty in their determination. Nevertheless, beyond the exact value of time constants, the comparison of the decays recorded for different sample solutions reveals trends as a function of solvent and presence of the nitro group.…”

mentioning

confidence: 95%

Two-Dimensional Electronic Spectroscopy Reveals Dynamics and Mechanisms of Solvent-Driven Inertial Relaxation in Polar BODIPY Dyes

Bolzonello

Polo

Volpato

et al. 2018

J. Phys. Chem. Lett.

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In this work, we demonstrate the use of two-dimensional electronic spectroscopy (2DES) to study the mechanism and time scale of the femtosecond Stokes shift dynamics in molecules characterized by intramolecular charge transfer, such as distyryl-functionalized boron dipyrromethene (BODIPY) molecules. The obtained results demonstrate that 2DES allows clear and direct visualization of the phenomenon. The analysis of the 2D data in terms of 2D frequency–frequency decay associated maps provides indeed not only the time scale of the relaxation process but also the starting and the final point of the energy flow and the associated reorganization energy, identified by looking at the coordinates of a negative signature below the diagonal. The sensitivity of the 2DES technique to vibrational coherence dynamics also allowed the identification of a possible relaxation mechanism involving specific interaction between a vibrational mode of the dye and the solvent.

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mentioning

confidence: 95%

Two-Dimensional Electronic Spectroscopy Reveals Dynamics and Mechanisms of Solvent-Driven Inertial Relaxation in Polar BODIPY Dyes

Bolzonello

Polo

Volpato

et al. 2018

J. Phys. Chem. Lett.

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“…Thus, using spectrally‐resolved pump‐probe technique, one can also envisage the idea of directly monitoring the time‐dependent gain in stimulated emission spectrum obviating the need of spectral reconstruction and estimation of time‐zero spectrum in non‐polar solvent, which we present in this work. It is worthy to mention here that spectrally‐resolved pump‐probe spectroscopy has been used to study synergistic behaviour in binary solvent mixtures and vibrational wavepacket interferometery measuring solvation in methanol and in proteins; two dimensional electronic spectroscopy has also been used to study solvation . Fluorescence correlation spectroscopy and time‐dependent Stokes shift was also implemented to study solvation dynamics in membranes .…”

Section: Introductionmentioning

confidence: 99%

“…It is worthy to mention here that spectrally-resolved pump-probe spectroscopy has been used to study synergistic behaviour in binary solvent mixtures [31] and vibrational wavepacket interferometery measuring solvation in methanol and in proteins; [32] two dimensional electronic spectroscopy has also been used to study solvation. [33,34] Fluorescence correlation spectroscopy and timedependent Stokes shift was also implemented to study solvation dynamics in membranes. [35] As discussed in the following section, extending our preliminary work [36] here we present experimental results which focuses on establishing a general method of studying solvation dynamics by spectrallyresolved degenerate pump-probe spectroscopy with a particular emphasis on estimating early time solvation dynamics.…”

Section: Introductionmentioning

confidence: 99%

Early Time Solvation Dynamics Probed by Spectrally Resolved Degenerate Pump‐Probe Spectroscopy

Silori

Seliya

2019

ChemPhysChem

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The dynamic role of solvent in influencing the rates of physico‐chemical processes (for example, polar solvation and electron transfer) has been extensively studied using time‐resolved fluorescence spectroscopy. Here we study ultrafast excited state relaxation dynamics of three different fluorescent probes (DNTTCI, IR‐140 and IR‐144) in two polar solvents, ethanol and ethylene glycol, using spectrally resolved degenerate pump‐probe spectroscopy. We discuss how time‐resolved emission spectra can be directly used for constructing relaxation correlation function, obviating spectral reconstruction and estimation of time‐zero spectrum in non‐polar solvents. We show that depending on the specific probe used, the relaxation dynamics is governed either by intramolecular vibrational relaxation (for IR140) or by intermolecular solvation (for DNTTCI) or by both (for IR144). We further show (using DNTTCI as a probe) that major differences in solvation by ethanol and ethylene glycol is contributed by early time (<1 ps) dynamics.

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“…The sensitivity of the 2DES technique to vibrational coherence dynamics also allowed the identification of a possible relaxation mechanism involving specific interaction between vibrational modes of the dye and the solvent. Also Lee and co-workers studied different BODIPY, i.e., BODIPY-2H and BODIPY-2I chromophores dissolved in methanol by applying 2DES [56]. The authors observed that after electronic excitation, the BODIPY molecules relax in response to the change in the charge distribution, through solvent reorganization and/or intra-and intermolecular vibrational energy redistribution.…”

Section: Recent Advances In Multidimensional Ultrafast Spectroscopy Amentioning

confidence: 99%

“…The authors observed ultrafast solvation dynamics of the two dyes on a sub-100 fs time scales. Furthermore, they demonstrated a new data analysis procedure for extracting the dynamic Stokes shift from 2DES spectra, focusing on monitoring the frequency changes associated with the SE, revealing an ultrafast solvent relaxation [56].…”

Section: Recent Advances In Multidimensional Ultrafast Spectroscopy Amentioning

confidence: 99%

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

et al. 2020

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The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.

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Ultrafast Solvation Dynamics and Vibrational Coherences of Halogenated Boron-Dipyrromethene Derivatives Revealed through Two-Dimensional Electronic Spectroscopy

Cited by 35 publications

References 108 publications

Two-Dimensional Electronic Spectroscopy Reveals Dynamics and Mechanisms of Solvent-Driven Inertial Relaxation in Polar BODIPY Dyes

Two-Dimensional Electronic Spectroscopy Reveals Dynamics and Mechanisms of Solvent-Driven Inertial Relaxation in Polar BODIPY Dyes

Early Time Solvation Dynamics Probed by Spectrally Resolved Degenerate Pump‐Probe Spectroscopy

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

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