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Investigation of non-Rehm-Weller kinetics in the electron transfer from trivalent phosphorus compounds to singlet excited sensitizers
Singlet excited states (1S* and 1S +*) of neutral and monocationic sensitizers, S and S +, respectively, were quenched by electron transfer (ET) from a variety of trivalent phosphorus compounds (Z3P). The quenching rate constants kq, which are equal to the rate constants kET of the ET from Z3P to 1S* or 1S+*, were determined by the Stern-Volmer method. The logarithm of kET was plotted against free-energy change DeltaG0 of the ET. The plot deviated upward from the line predicted by the Rehm-Weller (RW) theory in the endothermic region, the deviation being larger in the ET to a neutral acceptor 1S* than in the ET to a cationic acceptor 1S+*. Such a kinetic behavior is in sharp contrast to that observed in the ET from amines (R 3N), where the ET to either neutral or cationic acceptor takes place according to the RW prediction. The ET from a donor, Z3P or R 3N, to a neutral acceptor 1S* is a charge-separation type, during which electrostatic attraction between the donor and the acceptor is generated, whereas the ET to a cationic acceptor 1S+* is a charge-shift type, which results in neither electrostatic attraction nor repulsion. Difference in kinetics-energetics relationship by the type of ET, which is not recognized in the ET from R3N donor, becomes “visible” when Z 3P is used as a donor. Copyright 2013 John Wiley & Sons, Ltd. The rate constants kET of electron transfer from trivalent phosphorus compounds to singlet photoexcited sensitizers were determined by the Stern-Volmer method. LogkET-DeltaG0 plots were found to deviate upward from the line predicted by the Rehm-Weller theory, with deviation being larger in ET to neutral acceptors than in ET to cationic acceptors. Copyright
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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate