Bimolecular photoinduced electron transfer reactions in liquids under the gaze of ultrafast spectroscopy

Rosspeintner, Arnulf; Vauthey, Eric

doi:10.1039/c4cp03862b

Cited by 36 publications

(37 citation statements)

References 199 publications

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“…Differential encounter theory has been shown to be well suited for properly describing the dynamics of bimolecular photoinduced electron transfer processes in solution. 4,12,14,15,17,[26][27][28][29][30] According to this theory, the survival probability N(t) of the excited electron donor obeys the equation…”

Section: Theorymentioning

confidence: 99%

“…Intermolecular photoinduced electron transfer (PET) between a donor D and an acceptor A is typically observed as a quenching of the excited precursor (D * or A * ) and leads to the formation of a radical-ion pair (RIP), 2 D ·+ + 2 A ·− . [1][2][3][4] PET from precursors in the singlet excited state produces singlet RIPs due to the conservation of the total spin in elementary chemical reactions. However, RIPs initially produced in the singlet state can also undergo geminate charge recombination (CR) to the triplet neutral reactants, namely, 3 D * +A or D+ 3 A * .…”

Section: Introductionmentioning

confidence: 99%

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Magnetic field effect on ion pair dynamics upon bimolecular photoinduced electron transfer in solution

Feskov

Rogozina

Ivanov

et al. 2019

The Journal of Chemical Physics

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The dynamics of the ion pairs produced upon fluorescence quenching of the electron donor 9,10-dimethylanthracene (DMeA) by phthalonitrile have been investigated in acetonitrile and tetrahydrofuran using transient absorption spectroscopy. Charge recombination to both the neutral ground state and the triplet excited state of DMeA is observed in both solvents. The relative efficiency of the triplet recombination pathway decreases substantially in the presence of an external magnetic field. These results were analyzed theoretically within the differential encounter theory, with the spin conversion of the geminate ion pairs described as a coherent process driven by the hyperfine interaction. The early temporal evolution of ion pair and triplet state populations with and without magnetic field could be well reproduced in acetonitrile, but not in tetrahydrofuran where fluorescence quenching involves the formation of an exciplex. A description of the spin conversion in terms of rates, i.e., incoherent spin transitions, leads to an overestimation of the magnetic field effect.Published under license by AIP Publishing. https://doi.org/10.1063/1.5064802In fact, singlet-triplet spin conversion in RIPs could take place via several mechanisms. Beside the HFI mechanism, paramagnetic relaxation of the electronic spins, intersystem ARTICLE scitation.org/journal/jcp conversion of the RIP as a coherent process. The experimental results are the first to be presented. This is followed by a description of the theoretical model and finally by the analysis of the experimental data. ARTICLE scitation.org/journal/jcp the ion yield of photoinduced electron transfer reactions in solution," Helv. Chim. Acta 71, 93-99 (1988).

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Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Magnetic field effect on ion pair dynamics upon bimolecular photoinduced electron transfer in solution

Feskov

Rogozina

Ivanov

et al. 2019

The Journal of Chemical Physics

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“…Marcus theory describes non-adiabatic CT reaction rates, k CT , in terms of activation Gibbs free energy, , * CT ΔG electronic coupling between the initial and final states (CT integral), V DA , total reorganisation energy, , and thermal energy, kT: [9][10][11]…”

Section: Marcus Theory Development With Image Dipole Interactionsmentioning

confidence: 99%

Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues

Lee¹,

Xiao²,

Woo³

et al. 2017

Nature Mater

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Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7-that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

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“…However, the TRIR decays measured with higher quencher concentrations are non-exponential (Figure 5), as expected for a diffusion-assisted ET quenching process, when measured with a sufficiently high time resolution [38,39,40,41,42]. This is due to the different stages of the quenching; namely, the static, the transient and the stationary stages.…”

Section: Resultsmentioning

confidence: 54%

Halogen-Bond Assisted Photoinduced Electron Transfer

et al. 2019

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The formation of a halogen-bond (XB) complex in the excited state was recently reported with a quadrupolar acceptor–donor–acceptor dye in two iodine-based liquids (J. Phys. Chem. Lett. 2017, 8, 3927–3932). The ultrafast decay of this excited complex to the ground state was ascribed to an electron transfer quenching by the XB donors. We examined the mechanism of this process by investigating the quenching dynamics of the dye in the S1 state using the same two iodo-compounds diluted in inert solvents. The results were compared with those obtained with a non-halogenated electron acceptor, fumaronitrile. Whereas quenching by fumaronitrile was found to be diffusion controlled, that by the two XB compounds is slower, despite a larger driving force for electron transfer. A Smoluchowski–Collins–Kimball analysis of the excited-state population decays reveals that both the intrinsic quenching rate constant and the quenching radius are significantly smaller with the XB compounds. These results point to much stronger orientational constraint for quenching with the XB compounds, indicating that electron transfer occurs upon formation of the halogen bond.

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Bimolecular photoinduced electron transfer reactions in liquids under the gaze of ultrafast spectroscopy

Cited by 36 publications

References 199 publications

Magnetic field effect on ion pair dynamics upon bimolecular photoinduced electron transfer in solution

Magnetic field effect on ion pair dynamics upon bimolecular photoinduced electron transfer in solution

Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues

Halogen-Bond Assisted Photoinduced Electron Transfer

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