Time resolved study of three ruthenium(II) complexes at micellar surfaces: A new long excited state lifetime probe for determining critical micelle concentration of surfactant nano-aggregates

• Synthesis and excited state lifetime of three different ruthenium complexes are studied.
• At micelle surfaces, the surfactant head charge and that of the ruthenium center as well as the hydrophobic tail of the ancillary ligand of the complexes have a greater role in deciding the nature of the interaction and the excited state properties.
• Long lifetime of ruthenium complex with a long chain ligand in water is due to the coiling of the carbon chain of the ancillary ligand around the ruthenium center.
• At micelle surfaces this coiling of the carbon chain is lost due to the parallel alignment with surfactants and thus a quenching of the excited state lifetime.
• A novel technique for the determination of cmc by monitoring long excited state lifetime is first time reported.

Three different ruthenium complexes have been synthesized and their luminescence properties in different solvent environments are reported. Luminescence intensities and excited state lifetimes of Ru-I, Ru-II and Ru-III vary with solvent viscosity. The excited state lifetime of Ru-I linearly increases in the viscosity range 1.76–12,100 cP. Ru-II shows two linear increases: one in the low and another in the high viscosity ranges, whereas Ru-III illustrates a linear enhancement only in the low viscosity range. Interestingly, luminescence intensities and excited state lifetimes of Ru-I, Ru-II and Ru-III are found to be sensitive to nano-aggregation. However, the surfactant head charge and that of the ruthenium center as well as the hydrophobic tail of the ancillary ligand of the complexes have a great role in deciding the nature of the interaction and on the excited state properties at micellar surfaces. It is proposed that the long lifetime of Ru-III in water could be due to the coiling of the carbon chain of the ancillary ligand around the ruthenium center. At micelle surface, this coiling of the carbon chain is lost due to the parallel alignment with surfactants and thus quenching of the excited state lifetime is seen. Furthermore, it is shown that the variation of the excited state lifetime with respect to the change in surfactant concentration is a result of the formation of micelles from the surfactant monomer, thus, a novel technique for the determination of the critical micelle concentration (cmc) based on the long excited state lifetime of Ru-III located at the micellar nano-aggregates is reported.

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