Acid-Base and Electrochemical Properties of the MLCT Excited States and One-Electron-Reduced Forms of Ruthenium(II) Complexes Containing 2-(2'-Pyridyl)pyrimidine and 2,2'-Bipyridine in Aqueous Solution.
The acid-base and electrochemical properties of the MLCT excited states and the one-electron-reduced forms of the three Ru(bpy)(3)(-)()(p)()(pypm)(p)()(2+) complexes, where bpy = 2,2'-bipyridine, pypm = 2-(2'-pyridyl)pyrimidine, and p = 1-3, have been examined in aqueous solution; a determination has been made of the ground- and excited-state electrochemical potentials, the values of the pK(a) and deprotonation rate constants of the conjugate acids of the excited states and the one-electron-reduced complexes, and the kinetics of the second-order decays of the reduced species. Comparison is made with the behavior of the analogous 10 complexes of the form Ru(bpy)(3)(-)()(m)()(-)()(z)()(bpm)(m)()(bpz)(z)()(2+), where bpm = 2,2'-bipyrimidine, bpz = 2,2'-bipyrazine, m and z = 0-3, and m + z </= 3, which have been studied in detail before.
Casalboni
Fiorella
F
Istituto di Fotochimica e Radiazioni d'Alta Energia del CNR, Via P. Gobetti 101, 40129 Bologna, Italy, Department of Chemistry, Boston University, Boston, Massachusetts 02215, and Department of Chemistry, Wichita State University, Wichita, Kansas 67260.
Mulazzani
Quinto G.
QG
Clark
Catherine D.
CD
Hoffman
Morton Z.
MZ
Orizondo
Peter L.
PL
Perkovic
Marc W.
MW
Rillema
D. Paul
DP