jp068994o_si_002.cif (16.52 kB)

Reversible Interchange of Charge-Transfer versus Electron-Transfer States in Organic Electron Transfer via Cross-Exchanges between Diamagnetic (Donor/Acceptor) Dyads

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posted on 21.06.2007, 00:00 by Duoli Sun, Sergiy V. Rosokha, Jay K. Kochi
The choice of appropriate electron donors (D) and acceptors (A) allows for the first time the simultaneous observation of Mulliken charge-transfer states, [D,A], that can coexist in reversible equilibrium with electron-transfer states, {D+•,A-•}, for various diamagnetic organic redox dyads. The theoretical analysis based on the (two-state) Mulliken−Hush analysis of the intervalence optical transition, together with the spectral identification of the transient ion-radical pairs of D+• and A-•, leads to the construction of the unusual potential-energy surface consisting of a single minimum without any reorganizational barrier for electron-transfer cross-exchanges with driving forces close to the isergonic limit. The mechanistic implications of this direct demonstration of the facile charge-transfer/electron-transfer interchange are discussed.