Absorption and emission spectra and mean lifetimes (τm) of the luminescence of tris(2,2′-bipyridine)- and tris(1,10-phenanthroline)ruthenium(II) are reported. For the 2,2′-bipyridine complex, two weak absorption bands occurring at 15 050 and 18 550 cm−1 are assigned, respectively, to the 1A1→3T1 and 1A1→1T1 transitions of d—d type, and the intense luminescence with origin at 17 250 cm−1 (τm = 5.92 μsec) is assigned to 1T1→1A1 fluorescence. For the 1,10-phenanthroline complex, no intra-d transitions were observed in absorption, but the bright luminescence with origin at 17 700 cm−1 (τm = 9.93 μsec) was assigned to 1T1→1A1 fluorescence in analogy with the first compound. The energy levels are analyzed on the basis of an octahedral model, and empirical values for the Racah B and C parameters for Ru II and the crystal-field parameter Δ are evaluated. Possible uses of the compounds for laser applications are suggested.

Absorption and emission spectra of nine (4d)6 ruthenium(II) complexes dissolved in rigid glasses are reported. Tris(bipyridine), tris(o-phenanthroline), bis(tripyridine), and a series of cis-substituted bis(bipyridine) complexes of ruthenium(II) were synthesized. The cis substituents were cyanide, ethylenediamine, pyridine, oxalate, and chloride chosen for their order in the spectrochemical series. On the basis of the structures of the emission spectra, their energy relationships with charge-transfer absorption bands, and the lack of correlation between the energies of emission and predictions from crystal-field theory, it is proposed that the intense luminescence observed from all the complexes under excitation by ultraviolet light is charge transfer in nature.

Die Komplexe (I) werden durch Umsetzung von Ru(II) oder K‐hexachloroosmat(IV) mit den Bipyridyl‐ Liganden in siedendem Ethylenglykol und von Ru(II) mit den Phenanthrolin‐Liganden in siedendem Ethanol dargestellt.

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