The influence of π-conjugation on competitive pathways: charge transfer or electron transfer in new D–π–A and D–π–Si–π–A dyads

2016 ◽  
Vol 18 (33) ◽  
pp. 22921-22928 ◽  
Author(s):  
Yang-Jin Cho ◽  
Ah-Rang Lee ◽  
So-Yoen Kim ◽  
Minji Cho ◽  
Won-Sik Han ◽  
...  

Intramolecular charge transfer results in a partial charge transfer species (Dδ+–π–Aδ−). The disconnection of π-conjugation between the donor and acceptor causes a unit-electron transfer to form D˙+–π–Si–π–A˙− species.

2016 ◽  
Vol 4 (14) ◽  
pp. 2731-2743 ◽  
Author(s):  
Shunsuke Sasaki ◽  
Gregor P. C. Drummen ◽  
Gen-ichi Konishi

Twisted intramolecular charge transfer (TICT) is an electron transfer process that occurs upon photoexcitation in molecules that usually consist of a donor and acceptor part linked by a single bond.


1982 ◽  
Vol 37 (5) ◽  
pp. 649-652 ◽  
Author(s):  
N. Miyoshi ◽  
M. Ueda ◽  
K. Fuke ◽  
Y. Tanimoto ◽  
M. Itoh ◽  
...  

Singlet oxygen was generated by the photosensitization of erythrosine. The lifetime of singlet oxygen and the quenching rate constant for singlet oxygen by NaN3 were measured by a thermal lensing method in MeOH-H2O mixed solvents. The reciprocal of the lifetime increased linearly with the increase of the H2O mole fraction. Semi-log plot of the quenching constant against the reciprocal of the solvent polarity exhibited a linear relation. The quenching of the singlet oxygen by NaN3 may proceed through a partial charge-transfer intermediate. The activation energy for the quenching reaction of N3- + 1O2 →[N3·1O2-] increased with the increase of the solvent polarity. The lifetime was also measured in MeOH-ethyleneglycol mixed solvents, and its relation with viscosity was obtained


2014 ◽  
Vol 16 (11) ◽  
pp. 5440 ◽  
Author(s):  
Veronika Novakova ◽  
Petr Hladík ◽  
Tereza Filandrová ◽  
Ivana Zajícová ◽  
Veronika Krepsová ◽  
...  

2019 ◽  
Vol 21 (31) ◽  
pp. 17118-17125 ◽  
Author(s):  
Hajime Torii

Changes in the spectral intensities in the THz region are good probes for the non-electrostatic aspect of halogen bonding.


1974 ◽  
Vol 29 (6) ◽  
pp. 880-887 ◽  
Author(s):  
P. P. Schmidt

This paper reports a theory of the inner sphere-type electron transfer reaction. Inner sphere reactions, as opposed to the outer sphere variety, require that the solvate or ligand shells surrounding the electron donor and acceptor species undergo considerable change in the course of the electron transfer. In this paper we assume that the electron transfer step takes place in a molecular complex which exists in equilibrium with the reactants. The electron transfer step occurs as a non-radiative charge transfer-type transition. In this manner we treat the charge transfer kinetics, in particular, the evaluation of the reaction rate constant, in the same manner as is usual for non-radiative problems. The analysis leading to the rate constant expression is based on Yamamoto’s general chemical reaction rate theory. The rate constant expressions obtained are quite general, they hold for any degree of strength of coupling between subsystems comprising the entire system. The activation energy, in the Arrhenius form for the rate constant, shows a dependence on the energy (work) of formation of the intermediate charge transfer complex, on vibrational shift energies associated with the molecular motions of the ligands, and on solvent repolarization energies. The activation energy also shows an important dependence on coupling terms which link the vibrations of the molecular inner shell with the polarization states of the (assumed) dielectric continuum which surrounds the charge transfer participants. The approach we take in developing this theory we believe points the way towards the development of a more complete theory capable of accounting for the dynamics of the molecular reorganization leading to the intermediate charge transfer complex as well as accounting for the electron transfer step itself.


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