Issue 44, 2015

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

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.

Graphical abstract: Controllable molecular aggregation and fluorescence properties of 1,3,4-oxadiazole derivatives

Supplementary files

Article information

Article type
Paper
Submitted
06 Aug 2015
Accepted
13 Oct 2015
First published
14 Oct 2015
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. C, 2015,3, 11681-11688

Author version available

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

H. Wang, F. Chen, X. Jia, H. Liu, X. Ran, M. K. Ravva, F. Bai, S. Qu, M. Li, H. Zhang and J. Brédas, J. Mater. Chem. C, 2015, 3, 11681 DOI: 10.1039/C5TC02445E

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