Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface.

Photoinduced electron transfer in a rigid first generation triphenylamine core dendrimer substituted with a peryleneimide acceptor.

The electron-transfer process of a first generation dendrimer with a triphenylamine core substituted with one peryleneimide chromophore at the rim (N1P1) was investigated by steady-state and time-resolved spectroscopic techniques in two different solvents of medium and low polarity. Single photon counting experiments showed a fast charge separation and a thermally activated back reaction, which is uncommon for a polyaryl bridge or long-distance through-space electron transfer. The four exponential fluorescence decay can be traced to the presence of two subsets of molecules, which are constitutional isomers of N1P1.