Reversible Charge Migration in the Excited State of an Electron Donor-Donor-Acceptor System Detected via Delayed Charge Transfer Fluorescence

Abstract

Reversible charge migration in the excited state of an electron Donor-Donor-Acceptor system detected via delayed charge transfer fluorescence Willemse, R.J.; Verhoeven, J.W.; Brouwer, A.M. Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.

Molecular Dynamics Simulations of Bimolecular Electron Transfer: Testing the Coulomb Term in the Weller Equation

“…Experimental verifications of the Weller equation are scarce. In principle, Δ G ET could be determined from the equilibrium constant between reactants and products, whereas in practice, this is only possible for Δ G ET around zero. , It is also generally accepted that ET in this case is not complete, and the product should be considered as an exciplex rather than a pair of ions. − More direct determination of Δ G ET using time-resolved calorimetry was shown to be hampered by the estimation of the entropy change upon ET. − …”

Photoinduced electron transfer in isolated bichromophoric and solvated trichromophoric systems

“…While a complete analysis of the temperature-dependent photophysical behaviour of TCI=TC3 will be published separately [17,18], we wish to report that the inversion of the relative energies of the CS I and CS2 states indeed occurs in the trichromophores.…”

“…5), with a very pronounced change in the contribution of the fast (direct) and slow (delayed) components with a change in solvent. In principle, this allows us to analyse in great detail the relative energies of the CS 1 and CS2 states [ 17,18 ], thereby enabling quantification of the difference in solvation energy brought about by the well-defined change in charge separation distance between these states. In conclusion, the extension of the bichromophores 1-3 to the trichromophores TCI-TC3 has shown that the anilinovinylcyanonaphthalene D-A pair provides a useful combination for the realization of multistep long-range charge separation via the multipiperidine bridging scheme introduced in the trichromophores.…”

Two-Directional Photoinduced Electron Transfer in a Trichromophoric System

“…The basic unit in which electron transfer can be studied comprises a single electron donor and a single electron acceptor. To obtain a long-lived charge separation, bichromophoric systems have been extended to molecules with three or more chromophores in which stepwise electron transfer takes place. − A trichromophoric system comprising one donor and two acceptor chromophores can also be used to compare directly two different electron-transfer pathways. In a system designed in a configuration A1−D−A2, if the donor chromophore is part of the initially excited state, electron transfer can occur in two directions depending on the factors that influence the electron-transfer mechanism.…”