Chain-Length- and Solvent-Dependent Intramolecular Proton Transfer in Styrene-Amine Exciplexes

Lewis, Frederick D.; Reddy, G. D.; Bassani, Dario M.; Schneider, Siegfried; Gahr, Michael

doi:10.1021/ja00081a021

Cited by 61 publications

(30 citation statements)

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“…SB occurs on the timescale of solvent uctuations, whereas structural relaxation is comparatively slower. [68][69][70][71] The ensemble of experimental results suggests that photoexcitation of 18C6 leads to the population of a higher excitonic state with a large oscillator strength (Fig. 5, le).…”

Section: C6 and 18c63ba 2+mentioning

confidence: 98%

Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

et al. 2019

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Section: C6 and 18c63ba 2+mentioning

confidence: 98%

Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

et al. 2019

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“…[1][2][3][4][5][6] The primary reason for interests to this class of compounds is because they are the constituents of many of the important synthetic polymeric materials. Styrene is the building unit of the poly-͑p-phenylene vinylene͒ ͑PPV͒ class of conducting polymeric materials known for their electroluminescent and semiconducting properties.…”

Section: Introductionmentioning

confidence: 99%

Mass analyzed threshold ionization spectroscopy of p-fluorostyrene

Georgiev

Neusser

Chakraborty

2004

The Journal of Chemical Physics

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Adiabatic ionization energy (AIE) and two-color threshold ion vibrational spectra of p-fluorostyrene have been measured by mass analyzed threshold ionization (MATI) method via three different intermediate levels in the first excited state, vibrationless S1 origin, 42(1)41(1), and 23(1) vibronic levels. Features of the ion vibrational spectra indicates that the geometry of the molecular ion including the conformation of the vinyl chain in the ionic ground state (D0) is almost identical to that of its neutral ground state (S0), and ionization has very little effect on the vibrational potentials of the aromatic ring modes. Comparison of the AIE with the reported value of styrene shows that fluorination at the para position of the aromatic ring has little effect on energy of the electron ejected in ionization process from the styrene chromophore.

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“…Rigid spacers such as polycyclic hydrocarbons 1c and α-helical polypeptides 1d provide well-defined geometries, facilitating investigation of the distance dependence of electron-transfer processes. For systems with flexible polymethylene spacers, both intramolecular exciplex formation in nonpolar solvents and the kinetics of electron transfer in polar solvents are dependent upon the chain length. − Numerous donor−acceptor systems with short linear chain polymethylene spacers (four or fewer saturated carbons) have been investigated. In general, these systems display a maximum in the intramolecular exciplex fluorescence intensity for chain lengths of three carbons, similar to that observed for intramolecular arene−arene excimer formation (Hirayama's rule) …”

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confidence: 99%

Intramolecular Electron Transfer in Donor−Spacer−Acceptor Systems with Alkylamide Spacers

1998

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Intramolecular electron transfer and exciplex formation have been investigated for a family of styrenespacer-amine molecules in which the spacer consists of a rigid amide group in the middle of a flexible alkane chain. The amide is connected to the styrene by either one or two methylene units and to a trialkylamine by two to six methylene units. The dependence of electron-transfer kinetics and exciplex formation have been investigated as a function of the length of the spacer, the orientation of the amide, and the amine oxidation potential. Intramolecular quenching of the styrene fluorescence intensity and lifetime is observed for all of the styrene-spacer-amine molecules. Quenching of styrene fluorescence is accompanied by the appearance of intramolecular styrene-amine exciplex fluorescence in nonpolar solvents. The low energy of the exciplex fluorescence emission maximum in nonpolar solvents is attributed to internal solvation by the polar amide group. A maximum in the quantum yield for exciplex fluorescence and minimum in the styrene lifetime is observed for spacers with a total length of seven atoms, including the amide group. This unusual chain length dependence is attributed to the conformational requirements of the amide group.

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Chain-Length- and Solvent-Dependent Intramolecular Proton Transfer in Styrene-Amine Exciplexes

Cited by 61 publications

References 0 publications

Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

Mass analyzed threshold ionization spectroscopy of p-fluorostyrene

Intramolecular Electron Transfer in Donor−Spacer−Acceptor Systems with Alkylamide Spacers

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