Picosecond Photophysics of1,4‐Diphenyl‐butadiene inCondensed Phase. SolventAssisted Electronic LevelInversion

Rullière, C.; Declémy, A.; Kottis, Ph.

doi:10.1155/lc.5.185

Cited by 26 publications

(12 citation statements)

References 9 publications

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“…The observed changes could not be reconciled with the 2A, and lB, assignment of Rulliere et al 11 We proposed that some of the observed spectral variations could be attributed to differing relative amounts of s-cis and s-trans rotamers in the excited state (refer to Figure 1 for structures). This results from the shift with solvent polarizability of thegroundstate absorption spectra of DPB with respect to the excitation wavelength of 355 nm.…”

Section: Introductioncontrasting

confidence: 64%

Excited-state s-cis rotamers produced by extreme red edge excitation of all-trans-1,4-diphenyl-1,3-butadiene

Wallace-Williams¹,

Moeller²,

Goldbeck³

et al. 1993

J. Phys. Chem.

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The shapes of the fluorescence emission and lowest excited singlet-state absorption spectra of all-trans-1,4-diphenylbutadiene (DPB) in hydrocarbon solvents vary with excitation wavelength when exciting on the extreme red edge of the ground-state absorption spectrum. This contrasts with the wavelength independence observed for the excited singlet-state absorption and fluorescence emission spectra of 1,5-diphenyl-2,3,4,6,7,8-hexahydronaphthalene and for the fluorescence emission spectra of 1 ,Cdiphenyl-1,3-~yclopentadiene, s-trans and s-cis structural analogs of DPB, respectively. The spectral changes in DPB can be explained in terms of an excitation wavelength-dependent production of s-cis and s-trans rotamer populations in the excited state. The DPB fluorescence emission spectrum was resolved into s-cis and s-trans components. The vibronic structure of the s-cis fluorescence spectrum is similar to that of s-trans, but the band origin is red-shifted and there is a slightly larger amplitude on the red edge. The excited-state absorption spectrum of s-cis DPB appears to be red-shifted relative to that of s-trans DPB as well.

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Section: Introductioncontrasting

confidence: 64%

Excited-state s-cis rotamers produced by extreme red edge excitation of all-trans-1,4-diphenyl-1,3-butadiene

Wallace-Williams¹,

Moeller²,

Goldbeck³

et al. 1993

J. Phys. Chem.

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“…One-and twophoton absorption studies suggest that the 2'A, state is the lowest excited singlet state.1k2o However, the results of emission studies show that the emitting state of DPB is not very different from the absorbing state (i.e., 11B, state), suggesting that the llB, state is the lowest excited state in DPB.21 Rulliere et al have suggested that this anomaly can be explained by solvent-enhanced inversion of the exited-state energy levels. 22 They propose that the 21A, state is slightly below the 11B, state prior to photoexcitation and that, upon excitation, the two states invert with the assistance of the solvent. This inversion is believed to occur in -10 ps; the mechanism by which it takes place is thought to be related to twisting of the phenyl rings.…”

Section: Introductionmentioning

confidence: 99%

Solvent/Solute Interactions Probed by Picosecond Transient Raman Spectroscopy: Vibrational Dynamics and State Ordering in S1 1,4-Diphenyl-1,3-Butadiene

Morris¹,

Gustafson²

1994

J. Phys. Chem.

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We present the SI Raman spectra of 1,4-diphenyl-1,3-butadiene (DPB) in n-hexane and THF at three different probe wavelengths. We assign the Raman spectra of S1 DPB on the basis of gas-phase and low-temperature fluorescence spectra. Bands assignable to the llB, and 2lA, states from the gas-phase spectra are both present in solution. These results suggest that the state we are observing in solution is a mixed state, having both llB, and 2lA, character. Broad vibrational bands associated with the olefin region of DPB suggest that there is a distribution of s-trans conformers in SI DPB. We also observe mode-specific, solvent-dependent dynamics in the excited-state Raman spectra. In particular, the peak position and bandwidth of the mode associated with the C=C phenyl stretch change as the delay is increased. We suggest that the mode-specific dynamics are related primarily to vibrational relaxation in SI DPB.

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“…The picosecond time domain excited singlet state absorption spectra of DPB, 10 and of DPH and DPO, 11 were first reported by Rulliere and co-workers. These spectra agreed qualitatively with the lower resolution nanosecond spectra obtained by Goldbeck et al However, their time-resolved studies showed that spectra were generally time dependent, with intensities of absorption features at longer wavelengths growing in time relative to shorter wavelengths.…”

Section: Introductionmentioning

confidence: 86%

Femtosecond Studies of Electronic Relaxation, Vibrational Relaxation, and Rotational Diffusion in all-trans-1,8-Diphenyl-1,3,5,7-octatetraene

et al. 1999

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Femtosecond transient absorption studies of the excited singlet state dynamics of all-trans-1,8-diphenyl-1,3,5,7-octatetraene were conducted in various hydrocarbon solvents at room temperature using 390 nm excitation and probe wavelengths between 630 and 820 nm. Linear dichroism measurements show that one of the decay components (100−150 ps) arises from rotational diffusion. The solvent viscosity dependence is consistent with that interpretation. Transient absorptions of the S2 (1Bu) and S1 (2Ag) states show ultrafast S2 → S1 internal conversion (470−600 fs) in association with possible vibrational relaxation within S1 and S2 on similar time scales.

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Picosecond Photophysics of1,4‐Diphenyl‐butadiene inCondensed Phase. SolventAssisted Electronic LevelInversion

Cited by 26 publications

References 9 publications

Excited-state s-cis rotamers produced by extreme red edge excitation of all-trans-1,4-diphenyl-1,3-butadiene

Excited-state s-cis rotamers produced by extreme red edge excitation of all-trans-1,4-diphenyl-1,3-butadiene

Solvent/Solute Interactions Probed by Picosecond Transient Raman Spectroscopy: Vibrational Dynamics and State Ordering in S1 1,4-Diphenyl-1,3-Butadiene

Femtosecond Studies of Electronic Relaxation, Vibrational Relaxation, and Rotational Diffusion in all-trans-1,8-Diphenyl-1,3,5,7-octatetraene

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