Three-dimensional representations of photo-induced electron transfer rates in pyrene-(CH2)n-N,N′-dimethylaniline systems obtained by three electron transfer theories

Rujkorakarn, Rong; Tanaka, Fumio

doi:10.1016/j.jmgm.2008.09.008

Cited by 6 publications

(6 citation statements)

References 27 publications

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“…PyC3NMe2 is known to form intramolecular exciplexes whose emission intensity depends upon factors that include solvent polarity and temperature. , In all of the PAMA films, the ratios of monomer to exciplex emission intensities were much lower than those in isotropic solvents of similar polarity, such as ethyl acetate . These lower ratios are attributed to the very high microviscosities in the films that inhibit the motions of the propylene spacer that are necessary to bring the 1-pyrenyl and dimethylamino groups into the correct exciplex orientation. ,, …”

Section: Resultsmentioning

confidence: 98%

Effects of Temperature and Alkyl Groups of Poly(Alkyl methacrylate)s on Inter- and Intramolecular Interactions of Excited Singlet States of Pyrenyl Guest Molecules

2010

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Temperature-induced changes in the static and dynamic characteristics of the fluorescence from pyrene and N,N-dimethyl-3-(pyren-1-yl)propan-1-amine (PyC3NMe2) have been used to determine the locations and mobilities of these probes in the anisotropic environments provided by films of 5 poly(alkyl methacrylate) (PAMA) polymers in which alkyl is ethyl, butyl, isobutyl, cyclohexyl, and hexadecyl. Whereas emission from pyrene reports on the polarity of the guest sites and the ability of molecules to diffuse translationally between sites, emission from PyC3NMe2 yields information about the fluidity and the shape of the guest sites. Data have been obtained from 20 to >400 K, a range that spans the onsets of several relaxation processes in the hosts. Those data indicate that the pyrenyl groups reside near to ester functionalities in most of the PAMAs, although the distance from them (and the main chains) depends upon the bulkiness of the alkyl groups. Among the most important conclusions derived from this research is that the rates of segmental relaxation phenomena near the probe molecules--and not free volume, as was concluded previously from fluorescence measurements in polyethylene films--are the dominant contributors to the fluorescence changes. Of practical importance, changes in those rates have permitted the onset temperatures of many of the relaxation phenomena occurring in the vicinity of the probes to be located.

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Section: Resultsmentioning

confidence: 98%

Effects of Temperature and Alkyl Groups of Poly(Alkyl methacrylate)s on Inter- and Intramolecular Interactions of Excited Singlet States of Pyrenyl Guest Molecules

2010

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“…68 Estimates for some of these parameters (for charge separation) have been reported for a 'donorinversed' molecule (P1D), in which the amino unit is para relative to the CH2 linker (λ i = 0.543 eV; S = 0.65, ℎ𝜔 = 0.840 eV, 𝜔 = 6775 cm -1 ). 69 The Gibbs free energy for electron transfer in acetonitrile was evaluated experimentally to be -0.48 eV, and is also reported in this work.…”

Section: Energetic and Kinetic Considerations For Charge Separation And Recombination Pathwaysmentioning

confidence: 58%

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline

Bissesar¹,

Raamsdonk²,

Gibbons³

et al. 2021

Preprint

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The conformational dependence of the matrix element for spin-orbit coupling and of the electronic coupling for charge separation are determined for an electron donor-acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the (Semi-Classical) Marcus Theory for electron transfer. The spin-orbit coupling, which plays a significant role in charge recombination to the triplet state can be probed by (TD-)DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin-orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

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“…Interestingly, for a molecule very similar to PyrDMA, electron transfer parameters have been reported, using a very different (multi-parameter fitting) approach. For a 'donorinversed' molecule (P1D), in which the amino unit is para relative to the CH 2 linker, such parameters have been estimated (λ i = 0.543 eV; S = 0.65, hω = 0.840 eV, ω = 6775 cm −1 ) [70]. The Gibbs free energy for electron transfer in acetonitrile was evaluated experimentally to be −0.48 eV, and is also reported in this work.…”

Section: Solventmentioning

confidence: 78%

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline

et al. 2022

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The conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin–orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin–orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin–orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

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Three-dimensional representations of photo-induced electron transfer rates in pyrene-(CH2)n-N,N′-dimethylaniline systems obtained by three electron transfer theories

Cited by 6 publications

References 27 publications

Effects of Temperature and Alkyl Groups of Poly(Alkyl methacrylate)s on Inter- and Intramolecular Interactions of Excited Singlet States of Pyrenyl Guest Molecules

Effects of Temperature and Alkyl Groups of Poly(Alkyl methacrylate)s on Inter- and Intramolecular Interactions of Excited Singlet States of Pyrenyl Guest Molecules

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline

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