Abstract
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 forms a more ordered two-dimensional layered structure. A π-stacking structure is observed in both cases, and adjacent molecules in 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 a 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.
Original language | English (US) |
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Pages (from-to) | 11681-11688 |
Number of pages | 8 |
Journal | Journal of Materials Chemistry C |
Volume | 3 |
Issue number | 44 |
DOIs | |
State | Published - 2015 |
Externally published | Yes |
ASJC Scopus subject areas
- General Chemistry
- Materials Chemistry