Electron Tunneling through Water: Oxidative Quenching of Electronically Excited Ru(tpy)22+ (tpy = 2,2‘:6,2‘ ‘-terpyridine) by Ferric Ions in Aqueous Glasses at 77 K
Journal of the American Chemical Society2000Vol. 122(34), pp. 8187–8191
Citations Over TimeTop 10% of 2000 papers
Abstract
The luminescence lifetime of Ru(tpy)22+ (tpy = 2,2‘:6,2‘ ‘-terpyridine) is 8.0 μs in H2SO4/H2O and HSO3F/H2O glasses (25% v/v) at 77 K, and 10.2 μs in D2SO4/D2O (25% v/v). Addition of moderate concentrations of the powerfully oxidizing Fe(OH2)63+ ion to the glasses leads to accelerated and highly nonexponential *Ru(tpy)22+ decay kinetics. The quenching is attributed to electron transfer from *Ru(tpy)22+ to randomly dispersed Fe(OH2)63+ complexes. The luminescence decay kinetics and quantum yields in the three aqueous glasses indicate that the electron-transfer rate constants decrease from ∼1013 s-1 at van der Waals contact with an exponential distance decay constant of 1.68 ± 0.07 Å-1.
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