Electron transfer and solvation in 9,9′-bianthryl and derivatives: a sub-ps fluorescence upconversion study

Jurczok, Martin; Gustavsson, T.; Mialocq, J.C.; Rettig, Wolfgang

doi:10.1016/s0009-2614(01)00809-0

Cited by 24 publications

(32 citation statements)

References 33 publications

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“…A subpicosecond loss of the structure of the LE emission of BA was also observed by fluorescence up-conversion . This process was then followed by a red shift of the emission on the 20 ps time scale in ethanol.…”

Section: Electron-transfer Reactionsmentioning

confidence: 79%

“…A subpicosecond loss of the structure of the LE emission of BA was also observed by fluorescence up-conversion. 231 This process was then followed by a red shift of the emission on the 20 ps time scale in ethanol. The first step was assigned to a partial planarization of BA through inertial motion and a partial delocalization of the excitation over the two anthryl units, whereas the second step was ascribed to the ET process, in agreement with the interpretation of Martin et al 230 The excited-state dynamics of BA and of its cyano derivative were revisited by Kovalenko et al using transient absorption with 50 fs time resolution.…”

Section: Intramolecular Electron Transfermentioning

confidence: 99%

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Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

et al. 2016

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Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha-Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis-trans isomerizations, respectively.

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Section: Electron-transfer Reactionsmentioning

confidence: 79%

Section: Intramolecular Electron Transfermentioning

confidence: 99%

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

et al. 2016

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“…For BA in ethanol and butanol, a structured anthracene-type fluorescence spectrum is reported to transform into an unstructured emission spectrum in the subpicosecond domain. 206 It is also reported that, in imidazolium ILs, the time-resolved fluorescence spectrum of BA near the time origin exhibits a sharp peak at 420 nm which corresponds to that of the structured anthracene-type LE emission. 207 Moreover, a typical theoretical model assumes instantaneous formation of electric dipole moment by crossing the transition state.…”

Section: Et and Ct Reactions In Ilmentioning

confidence: 91%

Ultrafast solvation dynamics and charge transfer reactions in room temperature ionic liquids

Nagasawa

Miyasaka

2014

Phys. Chem. Chem. Phys.

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Room temperature ionic liquids (ILs) are a new type of solvent with peculiar properties. ILs are usually composed of an anion and a bulky cation with one or more alkyl chains to decrease the melting point. These structural peculiarities lead to the high viscosity and the heterogeneity of ILs, which could affect chemical reactions. In the present perspective, we will first introduce the experimentally observed nature of the heterogeneous liquid structure and then introduce recent developments in the study on electron transfer (ET) and charge transfer (CT) reactions in relation with the solvation and the heterogeneity of ILs. Because of the high viscosity of ILs, diffusive solvation is expected to be slow which could be the rate-limiting factor for ET and CT processes. However, ILs could provide a unique reaction field depending on the location of the solute within the heterogeneous liquid structure and the reaction could be faster than that expected from the bulk viscosity due to the fast fluctuation of the local environment.

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“…The presence of the PCT state is supported by the results of time-resolved UV/vis spectroscopy and time-resolved microwave conductivity measurements. From time-resolved UV/vis spectroscopy, it has been suggested that the CT reaction proceeds via an intermediate in polar solvents. ,− Time-resolved microwave conductivity measurements suggest that BA photoexcited in nonpolar solvents has a permanent dipole moment larger than zero. It has not been widely accepted, however, that the CT reaction proceeds in nonpolar solvents …”

Section: Introductionmentioning

confidence: 99%

Two Different Charge Transfer States of Photoexcited 9,9′-Bianthryl in Polar and Nonpolar Solvents Characterized by Nanosecond Time-Resolved Near-IR Spectroscopy in the 4500−10 500 cm⁻¹Region

et al. 2010

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Transient absorption spectra of 9,9'-bianthryl (BA) in heptane, in acetonitrile, and in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (bmimTf(2)N) are observed with a nanosecond time-resolved near-IR absorption spectrometer for the wavenumber range of 4500-10,500 cm(-1) (2200-950 nm). In nonpolar heptane solution, a broad absorption band is observed at 6700 cm(-1) (1500 nm), in addition to a strong absorption band of the locally excited (LE) state centered at 9800 cm(-1) (1020 nm). The broad band is assigned to a partial charge transfer (PCT) band. The decay time constants of the PCT band and the LE band are both (13 +/- 1) ns. The agreement of the two decay constants strongly suggests that the PCT state is in equilibrium with the LE state in heptane. In acetonitrile, an absorption band of the charge transfer (CT) state is observed at 8000 cm(-1) (1250 nm). This band decays in (41 +/- 2) ns. In bmimTf(2)N, the CT band appears at 8500 cm(-1) (1180 nm) and decays in (34 +/- 1) ns. The difference in peak position for the CT bands in acetonitrile and in bmimTf(2)N, and the PCT bands in heptane, is explained well by the model based on the charge resonance between the two equivalent electronic structures of the CT state.

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Electron transfer and solvation in 9,9′-bianthryl and derivatives: a sub-ps fluorescence upconversion study

Cited by 24 publications

References 33 publications

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast solvation dynamics and charge transfer reactions in room temperature ionic liquids

Two Different Charge Transfer States of Photoexcited 9,9′-Bianthryl in Polar and Nonpolar Solvents Characterized by Nanosecond Time-Resolved Near-IR Spectroscopy in the 4500−10 500 cm⁻¹Region

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Electron transfer and solvation in 9,9′-bianthryl and derivatives: a sub-ps fluorescence upconversion study

Cited by 24 publications

References 33 publications

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast solvation dynamics and charge transfer reactions in room temperature ionic liquids

Two Different Charge Transfer States of Photoexcited 9,9′-Bianthryl in Polar and Nonpolar Solvents Characterized by Nanosecond Time-Resolved Near-IR Spectroscopy in the 4500−10 500 cm−1Region

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Two Different Charge Transfer States of Photoexcited 9,9′-Bianthryl in Polar and Nonpolar Solvents Characterized by Nanosecond Time-Resolved Near-IR Spectroscopy in the 4500−10 500 cm⁻¹Region