Controllable molecular aggregation and fluorescence properties of 1,3,4-oxadiazole derivative

The molecular self-assembly behaviour of 2,2’-Bis-(4-hexyloxyphenyl)-bi-1,3,4-oxadiazole (BOXD-6) in solution, on surfaces and in bulk crystals, and its photo-physical properties were studied via a combination of experimental techniques and theoretical calculations. It is found that BOXD-6 molecules self-assemble into both H- and J-aggregates at moderate concentration (~10-4 M) and then transit to exclusive J-aggregates at higher concentration (~10-3 M) in tetrahydrofuran. In H-aggregation (α polymorph), BOXD-6 adopts a linear conformation and forms a one- dimensional layered structure; in J-aggregation (β polymorph), it adopts a Z-shaped conformation and form a more ordered two-dimensional layered structure. A π-stacking structure is observed in both cases, and adjacent molecules in the J-aggregation show larger displacement along the molecular long axis direction than that in H-aggregation. Although J-aggregates are almost the only component in concentrated solutions (10-3 M), both H- and J-aggregates can be obtained if concentrated solution is transformed onto substrates through a simple drop-casting method. Such a phase transition during film formation can be easily avoided by adding water as precipitator; a film with pure J-aggregates is then obtained. In order to get more information on molecular self-assembly, intermolecular interaction potential energy surfaces (PES) were evaluated via theoretical calculations at the DFT level (M062x/6-31G**). The PES not only confirm the molecular stacking structures found in crystals but also predict some other likely structures, which will be the target of future experiments.