Unveiling Excited-State Chirality of Binaphthols by Femtosecond Circular Dichroism and Quantum Chemical Calculations

Schmid, Marco; Martínez‐Fernández, Lara; Markovitsi, Dimitra; Santoro, Fabrizio; Hache, F.; Improta, Roberto; Changenet‐Barret, Pascale

doi:10.1021/acs.jpclett.9b00948

Cited by 35 publications

(49 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This also enables the conduction of a kinetics study by means of the time-resolved probe, helping us to gain more insight into the associated mechanism. 14 , 33 − 39 …”

Section: Introductionmentioning

confidence: 99%

Counterion Migration Driven by Light-Induced Intramolecular Charge Transfer

Lin

Liu

et al. 2021

JACS Au

View full text Add to dashboard Cite

A series of D−π– A + pyridinium compounds, in which D = −NPh 2 and A + = −PyMe + are linked by various amounts of linear phenyl spacers, were strategically designed and synthesized. Their characterization revealed the presence of excited-state intramolecular charge transfer (ESICT) that triggers a corresponding response from the counterion. In medium and strong polar solvents, the fast solvent relaxation occurring after ESICT overwhelms the counterion effect, showing typical emission solvatochromism. In weakly polar solvents, ESICT induces counteranion migration for electrostatic stabilization, the time scale of which is dependent on the radius of the counteranion, the length of the π-linker, and the viscosity of the solvent. In low-viscosity organic solvents such as toluene, counteranion migration occurs within several tens to hundreds of picoseconds, resulting in a time-dependent continuous emission that can be resolved from the spectral temporal evolution. Concrete evidence for this is provided by the chemical synthesis of a D−π– A + pyridinium–sulfur trioxide – zwitterion, where anion migration is restricted due to its internally locked ion pair. As a result, only a single emission band can be observed. These comprehensive studies prove that the ion migration process may be significant for a wide range of ESICT-type ionic fluorophores. Such an ionic movement, triggered by optically pumped ESICT of the D−π– A + dyad, is similar to the molecular machine driven by the redox reaction, but with a facile access and fast response.

show abstract

“…This also enables the conduction of a kinetics study by means of the time-resolved probe, helping us to gain more insight into the associated mechanism. 14 , 33 − 39 …”

Section: Introductionmentioning

confidence: 99%

Counterion Migration Driven by Light-Induced Intramolecular Charge Transfer

Lin

Liu

et al. 2021

JACS Au

View full text Add to dashboard Cite

show abstract

“…The steady-state and time-resolved ECD spectra of binol have been measured by Hache and coworkers in different solvents. 39,43,81 Niezborala and Hache report the steady-state spectrum of R-binol in ethanol, whereas the one of S-binol in cyclohexane was reported by Schmid et al f lg = 0.0001). We summarize in Table 1 our results for energies, oscillator strengths, and rotatory strengths of the L a and L b states of the R a and S a structures considered here, using EOM-CCSD and CAM-B3LYP and two different basis sets.…”

Section: Binolmentioning

confidence: 93%

Probing Molecular Chirality of Ground and Electronically Excited States in the UV-vis and X-ray Regimes: An EOM-CCSD Study

Andersen

Nanda

Krylov

et al. 2021

Preprint

View full text Add to dashboard Cite

We present several strategies for computing electronic circular dichroism (CD) spectra across different frequency ranges at the equation-of-motion coupled-cluster singles and doubles level of theory. CD spectra of both ground and electronically excited states are discussed. For selected cases, the approach is compared with coupled-cluster linear response results as well as time-dependent density functional theory. The extension of the theory to include the effect of spin-orbit coupling is presented and illustrated by calculations of X-ray CD spectra at the L edge.

show abstract

“…26 In other cases, quantum chemical calculations can help interpreting the TRCD measurements. 27,28 This issue is of primary importance for single-wavelength experiments but will be less so when broadband measurements can be performed routinely. Indeed, comparing the full CD spectra before and after photoexcitation and using standard techniques such as SVD will be very informative in future experiments.…”

Section: A Brief History Of the Development Of Ultrarapid Trcdmentioning

confidence: 99%

Multiscale conformational dynamics probed by time‐resolved circular dichroism from seconds to picoseconds

Hache

Changenet‐Barret

2021

Chirality

Self Cite

View full text Add to dashboard Cite

Time-resolved circular dichroism has been developed for a few decades to investigate rapid conformational changes in (bio)molecules. In our group, we have come up with several experimental set-ups allowing us to study piconanosecond local phenomena in molecular systems as well as much slower effects occurring in proteins and DNA in the folding processes. After an overview of the worldwide realizations in this domain, we present emblematic experiments that we have carried out, spanning time domain from picoseconds to seconds.

show abstract

Unveiling Excited-State Chirality of Binaphthols by Femtosecond Circular Dichroism and Quantum Chemical Calculations

Cited by 35 publications

References 35 publications

Counterion Migration Driven by Light-Induced Intramolecular Charge Transfer

Counterion Migration Driven by Light-Induced Intramolecular Charge Transfer

Probing Molecular Chirality of Ground and Electronically Excited States in the UV-vis and X-ray Regimes: An EOM-CCSD Study

Multiscale conformational dynamics probed by time‐resolved circular dichroism from seconds to picoseconds

Contact Info

Product

Resources

About