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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 9, Number 5
May 20, 1988 

Precipitation, Resolubilization and Luminescent Properties of Tris (2,2'-diimine)Ruthenium(Ⅱ) Complexes in Premicellar Anionic Surfactant Solutions
Joon Woo Park*, Sung Hee Kim
Premicellar precipitation, resolubilization and luminescing behaviors of RuL32+ (L = bpy, phen, Me2bpy) in aqueous alkylsulfate and sulfonate solutions were studied. Addition of the anionic surfactants to RuL32+ solutions caused initial precipitation which was redissolved by further addition of the surfactants. The apparent solubility products Ksp's of the precipitates were evaluated assuming 1:2 salt formation. The values were smaller as the ligand is more hydrophobic and the length of hydrocarbon chain of the surfactant is longer. The Ksp values for L = bpy were constant over wide surfactant concentration range. However, those for L = Me2bpy and also for phen, but to less extent, increased with the surfactant concentration. The resolubilization of 1:2 salts was followed by red-shift of emission band and extensive emission quenching above critical concentration of the surfactants. The critical concentration was lower for more hydrophobic surfactant. For L = Me2bpy, the blue-shifted emission band with enhanced emission intensity was observed in intermediate surfactant concentration region. The high ionic strength of media prevented the precipitate formation, but facilitated the red-shift of the emission bands. The results support that the precipitate is dissolved by accretion of surfactant anions to the salts to form water-soluble surfactant-rich RuL3-surfactant anionic species. These species appeared to aggregate cooperatively to produce large clusters which exhibited the red-shifted emission.
317 - 322
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