Thermodynamic Constants and Rate Constants of the Formation of the Pyrene Dimer Cation

Arai, Shigeyoshi; Kira, Akira; Imamura, Masashi

doi:10.1063/1.1677440

Cited by 10 publications

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“…A spectrum somewhat similar to that of Ethene 2 •+ in Figure is observed in chloroform (Figure S2), but this spectrum appears to be overlapped by that of another species. Some earlier experiments on cations of aryls have been able to observe the decay of monomer cations and formation of dimers. , Figures S3 and S4 show data observing monomer decay and dimer growth for naphthalene cations in DCM. We did not succeed in observing those kinetics for Ethene 2 •+ .…”

Section: Resultsmentioning

confidence: 91%

“…Some earlier experiments on cations of aryls have been able to observe the decay of monomer cations and formation of dimers. 15,16 Figures S3 and S4 show data observing monomer decay and dimer growth for naphthalene cations in DCM. We did not succeed in observing those kinetics for Ethene (DCM •+ ) formed by ionization of the solvent.…”

Section: Figure 1 Displays Transient Absorption Spectra Of Napmentioning

confidence: 99%

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Kinetics and Energetics of Electron Transfer to Dimer Radical Cations

2023

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Spectra of the dimer cations naphthalene (Nap 2 •+ ) and ethene (Ethene 2•+ ) were measured in liquid dichloromethane (DCM). The spectra peak at very different energies, 1.2 and 3.3 eV. In DCM dimerization stabilizes Nap 2•+ by ΔG d °(Nap 2 •+ ) = −218 meV relative to the monomer Nap •+ as determined from the dimerization equilibrium constant. Both dimers can transfer a positive charge to hole acceptor molecules, but for both the rate constants rise more gradually with reaction energetics than do many charge transfer reactions previously studied. A striking observation finds that the rate constant for hole transfer from the Nap 2•+ dimer to phenanthrene is smaller by two decades than that from biphenyl •+ monomer to Nap, although both reactions have the same −ΔG°= 0.05 eV. A plausible interpretation for these observations is the presence of an energy of reorganization, λ(M 2 ), for the dimer that involves movement apart of the two partners in the dimer. While the dimerization equilibrium cannot be measured for Ethene 2•+ , the charge transfer data imply that both ΔG d °(Ethene 2 •+ ) and λ(Ethene 2•+) are considerably larger, perhaps by factors of 2−4 than for Nap 2•+ .

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Section: Resultsmentioning

confidence: 91%

Section: Figure 1 Displays Transient Absorption Spectra Of Napmentioning

confidence: 99%