Abstract
Interactions between the MLCT excited states of Ru(bpy)32+ (bpy = 2,2‘-bipyridine) or Ru(bpz)32+ (bpz = 2,2‘-bipyrazine) and phenol or monochlorophenols have been investigated in aqueous solution using steady-state and time-resolved spectrofluorimetry. The presence of phenol (PhOH), which does not quench *Ru(bpy)32+ in mildly acidic solution, causes the emission to undergo a blue shift with increasing [PhOH]; the emission quantum yields and the excited-state lifetimes decrease with increasing [PhOH] at low temperatures (5−35 °C) but increase with increasing [PhOH] at higher temperatures (35−70 °C). This behavior is understood in terms of the variations in the rate constants of the temperature-independent radiative and nonradiative decays of *Ru(bpy)32+ and the activation-controlled population of the metal-centered excited state as [PhOH] is changed. The presence of chlorophenols has no effect on the photophysics of *Ru(bpy)32+; PhOH reductively quenches *Ru(bpz)32+.
Published Version
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