Cyclodextrin cavity size effect on the complexation and rotational dynamics of the laser dye 2,5-diphenyl-1,3,4-oxadiazole: from singly occupied complexes to their nanotubular self-assemblies.

The general complexation scheme as well as the dynamic features of the supramolecular structures resulting from the interaction of the laser dye 2,5-diphenyl-1,3,4-oxadiazole (PPD) with the naturally occurring alpha-, beta-, and gamma-cyclodextrins in water are studied by means of fluorescence spectroscopy, both steady-state (SS) and time-resolved (TR). PPD interacts weakly, from a thermodynamic point of view, with alpha-cyclodextrin (alpha-CD), forming 1:1 complexes with an association constant of K(11) = 85 +/- 4 M(-1). However, the local motion of the substrate (PPD) with respect to the ligand (CD) in the complexed form is hindered; namely, dynamically, they are strongly coupled and only a global tumbling motion, = 370 +/- 30 ps, of the whole adduct is observed. The next homologue beta-CD also forms 1:1 entities with PPD, but although the binding strength of reactants (K(11) = 682 +/- 60 M(-1)) is almost an order of magnitude greater than the former case with the alpha-CD, these are dynamically weakly coupled. In fact, two independent motions are detected: one is that of the whole nanostructure motion (1:1, PPD/beta-CD) with a global rotational relaxation time of = 480 +/- 30 ps, and the other is an internal librational motion of the dye inside the host cavity with an average angular displacement of theta approximately 27 degrees . Finally, the interaction of PPD with the wider and more flexible cavity of the gamma-CD "triggers" a self-associative scheme of the initially formed supramolecular building blocks, namely, singly occupied complexes, leading to the formation of nanotubular superstructures. It is found that these linear arrays are constituted from more than 17 gamma-CD units which are held together with the aid of dimers of PPD. Interestingly, our results supported that two distinct dimeric forms of PPD play the role of the "shaft" between adjacent cyclodextrin units. The topology of the dimers in the interlinking space of gamma-CD units is such that PPD molecules are held in suitable proximity, resulting, upon excitation, in the observation of dual excimer emission.