Micellar effects on the molecular aggregation and fluorescence properties of benzazole-derived push–pull butadienes

The absorption and fluorescence spectral behaviour of 1-(2-benzoxazolyl)-4-(p-dimethylaminophenyl)buta-1,3-diene and its benzothiazolyl analogue (abbreviated as BODB and BTDB, respectively) have been investigated in dioxane–water mixtures and micellar environments using steady-state techniques. In water, water-rich mixtures or premicellar solutions, BODB and BTDB tend to form molecular aggregates labelled as H-aggregates. These aggregates dissociate on adding surfactants forming micellized monomers. In all micellar media the fluorescence quantum yield is greatly enhanced along with a large hypsochromic shift. Also, in TX-100, CTAB and SDS both dienes show dual emission from the locally excited (LE) and intramolecular charge transfer (ICT) states. For BTDB in TX-100 and DODB in all solutions, the LE fluorescence predominates, while for BTDB in CTAB and SDS, the ICT fluorescence is the predominant. The fluorescence shifts suggest that the fluorescing molecules penetrate the core of the micellar unit in TX-100, whereas in CTAB and SDS they occupy the interfacial region. The binding constants and the micelle properties (such as polarity and CMC) have been determined using both dienes as probes.