Journal ArticleDOI
Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer
Dieter Rehm,Albert Weller +1 more
TLDR
In this article, the rate constants of 60 typical electron donor-acceptor systems have been measured in de-oxygenated acetonitrile and are shown to be correlated with the free enthalpy change, ΔG23, involved in the actual electron transfer process.Abstract:
Fluorescence quenching rate constants, kq, ranging from 106 to 2 × 1010 M−1 sec−1, of more than 60 typical electron donor-acceptor systems have been measured in de-oxygenated acetonitrile and are shown to be correlated with the free enthalpy change, ΔG23, involved in the actual electron transfer process
in the encounter complex and varying between + 5 and −60 kcal/mole. The correlation which is based on the mechanism of adiabatic outer-sphere electron transfer requires ΔG≠23, the activation free enthalpy of this process to be a monotonous function of ΔG23 and allows the calculation of rate constants of electron transfer quenching from spectroscopic and electrochemical data.
A detailed study of some systems where the calculated quenching constants differ from the experimental ones by several orders of magnitude revealed that the quenching mechanism operative in these cases was hydrogen-atom rather than electron transfer.
The conditions under which these different mechanisms apply and their consequences are discussed.read more
Citations
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Signaling Recognition Events with Fluorescent Sensors and Switches.
A. Prasanna de Silva,H. Q. Nimal Gunaratne,Thorfinnur Gunnlaugsson,Allen J. M. Huxley,Colin P. McCoy,Jude T. Rademacher,Terence E. Rice +6 more
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Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence
Alberto Juris,Vincenzo Balzani,F. Barigelletti,Sebastiano Campagna,Peter Belser,A. Von Zelewsky +5 more
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BODIPY dyes and their derivatives: syntheses and spectroscopic properties.
Aurore Loudet,Kevin Burgess +1 more
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Progress in the development of a Reynolds-stress turbulence closure
TL;DR: In this article, the authors developed a model of turbulence in which the Reynolds stresses are determined from the solution of transport equations for these variables and for the turbulence energy dissipation rate E. Particular attention is given to the approximation of the pressure-strain correlations; the forms adopted appear to give reasonably satisfactory partitioning of the stresses both near walls and in free shear flows.
Journal ArticleDOI
Organic Photoredox Catalysis
TL;DR: An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.
References
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Journal ArticleDOI
Correlating Diffusion Coefficient in Liquids
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Charge‐Transfer Complex and Solvent‐Shared Ion Pair in Fluorescence Quenching
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Oxidation, reduction, and electrochemiluminescence of donor-substituted polycyclic aromatic hydrocarbons
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Electroorganic Preparations. IV. Oxidation of Aromatic Hydrocarbons.
Journal ArticleDOI
Electronic processes in hetero-excimers and the mechanism of fluorescence quenching
TL;DR: In this article, the electronic processes of charge transfer type complex of pyrene and N, N-dimethylaniline, which is formed only in the electronically excited state, have been studied.