Nonthermalized excited states in Ru(II) polypyridyl complexes probed by ultrafast transient absorption spectroscopy with high photon energy excitation

The picosecond excited state dynamics of a series of homoleptic Ru(II) polypyridyl complexes (where LL = bpy, dmb, dmeob, dfmb, or dttb) have been investigated in aqueous solution at room temperature using femtosecond transient absorption spectroscopy with high photon energy excitation. All of the complexes studied produced similar spectroscopic signatures: a near-instantaneous bleach centered at 470–500 nm corresponding to the static absorption spectrum, as well as an intense absorption (475–650 nm) that decayed within the instrument response function (IRF) to form a broad, low-level absorption extending from 500–650 nm. Detailed analyses of both kinetic and spectral parameters by singular value decomposition (SVD) indicate that the excited state difference spectra contain contributions from at least three distinguishable species that have been assigned as ligand-based π* ← π* and ligand-to-metal-charge-transfer (LMCT) transitions concomitant with the loss of the ground state metal-to-ligand-charge-transfer (MLCT) transition. Kinetic information extracted at 530 nm (an optical marker for the fully intraligand-delocalized 3MLCT state) or 660 nm (LMCT transitions) appear to be biphasic in some cases with the amplitude of the IRF-limited component becoming larger with shorter wavelength excitation. Further, rise dynamics were observed at redder probe wavelengths for Ru(bpy)32+ and Ru(dttb)32+. These observations are different from those obtained using lower photon energy excitation and show that excitation wavelength strongly influences the early photophysical events in these Ru(II) complexes.Key words: ruthenium, photophysics, lasers, transient absorption spectroscopy, excited states, singular value decomposition (SVD).