Preparation, Photochemistry, and Electronic Structures of Coumarin Laser Dye Complexes of Cyclopentadienylruthenium(II)

Robert S. Koefod, Kent R Mann

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The syntheses and characterization of six new compounds that contain the CpRu+(Cp = η5-C5H5) moiety bound to a substituted coumarin laser dye are reported. The complexes prepared are of the general form [CpRu(η6-laser dye)]PF6, where laser dye = coumarin-1 (7-(diethylamino)-4-methylcoumarin), coumarin-2 (4,6-dimethyl-7-(ethylamino)coumarin), coumarin-6 (3-(2-benzothiazolyl)-7-(diethylamino)coumarin), coumarin-311 (7-(dimethylamino)-4-methylcoumarin), coumarin-334 (10-acetyl-2,3,6,7-tetrahydro-1H,5H,l lH-[l]benzopyrano[6,7,8-(ij]quinolizin-l0-one), or coumarin-338 (2,3,6,7-tetrahydro-l 1-oxo-lH,5H,l1H-[l]benzopyrano[6,7,8-ij]quinolizine-10-carboxylic acid 1,1-dimethylethyl ester). The structures of all of the new complexes except the complex of coumarin-6 were determined bylH and13C NMR spectroscopy and contain the CpRu+group bound to the benzenoid moiety of the coumarin system. The CpRu+group binds to the benzothiazole group of the coumarin-6 compound. Photolysis of the complexes in CH3CN solutions results in the formation of CpRu(CH3CN)3 + and the free dye. The complexes of the dyes other than coumarin-6 exhibit low-lying MLCT bands and are not emissive. The coumarin-6 complex retains the low-lying intramolecular charge-transfer band present in the free dye and emits in fluid solution at room temperature with ⋋max= 532 nm and Φ = 0.11 ± 0.02. The laser dye centered emission band of the complex is red-shifted 25 nm with respect to the free coumarin-6 emission.

Original languageEnglish (US)
Pages (from-to)2285-2290
Number of pages6
JournalInorganic Chemistry
Issue number12
StatePublished - Jun 1 1989


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