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The ultrafast relaxation of aq. Fe(II)-tris(bipyridine) upon excitation into the singlet metal-to-ligand charge-transfer band (1MLCT) was characterized by femtosecond fluorescence up-conversion and transient absorption (TA) studies. The fluorescence expt. shows a very short-lived broad 1MLCT emission band at .apprx.600 nm, which decays in ?20 fs, and a weak emission at .apprx.660 nm, which the authors attribute to the 3MLCT, populated by intersystem crossing (ISC) from the 1MLCT state. The TA studies show a short-lived (