Fluorescence Dynamics of Coumarin C522 as a Function of Micelle Confinement along with Cyclodextrin Supramolecular Complex Formation



Our aim is to doubly confine a molecule of coumarin C522 in a host–guest supramolecular complex with β-cyclodextrin in a reverse sodium dioctyl sulfosuccinate (AOT) micelle using nonpolar n-heptane and polar water solvents. Varying the volumes of coumarin C522 and β-cyclodextrin dissolved in water allows us to control the water-pool diameters of the reverse micelle in n-heptane with values of w=3, 5, 10, 20, and 40, where w is the ratio of water concentration to AOT concentration in n-heptane. To study the fluorescence dynamics of coumarin C522, the spectral steady-state and time-resolved dependences are compared for the two systems coumarin C522(water)/AOT(n-heptane), denoted C522/micelle, and coumarin C522/β-cyclodextrin(water)/AOT(n-heptane), referred to as C522/CD/micelle. The formation of the supramolecular host–guest complex CD–C522 is indicated by a blue shift, but in the micelle, the shift is red. However, the values of the fluorescence maxima at 520 and 515 nm are still way below the value of 535 nm representing bulk water. The interpretation of the red shift is based on two complementary processes. The first one is the confinement of CD and C522 by the micelle water pool and the second is the perturbation of the micelle by CD and C522, resulting in an increase of the water polarity. The fluorescence spectra of the C522/micelle and C522/CD/micelle systems have maxima and shoulders. The shoulder intensities at 440 nm, representing the C522 at n-heptane/AOT interface, decrease as the w values decrease. This intensity shift suggests that the small micelle provides a stronger confinement, and the presence of CD shifts the equilibrium from n-heptane towards the water pool even more. The fluorescence emission maxima of the C522/micelle and C522/CD/micelle systems for all w values clearly differentiate two trends for w=3–5, and w=10–40, suggesting different interaction in the small and large micelles. Moreover, these fluorescence maxima result in 7 and 13 nm differences for w=3 and w=5, respectively, and provide the spectral evidence to differentiate the C522 confinement in the C522/micelle and C522/CD/micelle systems as an effect of the CD molecule, which might be interpreted as a double confinement of C522 in CD within the micelle. The ultrafast decay in the case of w=3 ranges from 9.5 to 16 ps, with an average of 12.6 ps, in the case of the C522/micelle system. For C522/CD/micelle, the ultrafast decay at w=3 ranges from 9 to 14.5 ps, with an average of 11.8 ps. Increasing w values (from 10 to 40) result in a decrease of the ultrafast decay values in both cases to an average value of about 6.5 ps. The ultrafast decays of 12.6 and 11.8 ps for C522/micelle and C522/CD/micelle, respectively, are in the agreement with the observed red shift, supporting a double confinement in the C522/CD/micelle(w=3) system. The dynamics in the small and large micelles clearly show two different trends. Two slopes in the data are observed for w values of 3–5 and 10–40 in the steady-state and time-resolved data. The average ultrafast lifetimes are determined to be 12.6 and 6.5 ps for the small (w=3) and the large (w=40) micelles, respectively. To interpret the experimental solvation dynamics, a simplified model is proposed, and although the model involves a number of parameters, it satisfactory fits the dynamics and provides the gradient of permittivity in the ideal micelle for free water located in the centre (60–80) and for bound water (25–60). An attempt to map the fluorescence dynamics of the doubly confined C522/CD/micelle system is presented for the first time.