Computational modeling and self-assembly synthesis of borazine-based free-standing molecular-thin films

Calvani, D.; Jiao, A.; Kock, T.J.F.; Siegler, M.A.; Sai Sankar Gupta, K.B.; Filippov, D.V.; Groot, H.J.M. de; Sevink, G.J.A.; Schneider, G.F.; Buda, F.

doi:doi:10.1021/acs.langmuir.5c05963

Boron-nitride-rich organic thin materials based on borazines have gained significant attention for their potential in nano(opto)electronic and energy storage devices. We address synthetic challenges in producing effective borazine-based thin films by proposing a dual theoretical and experimental protocol. This combines a multiscale computational approach, using density functional theory and classical molecular dynamics, with synthesis and thin-film formation via the Langmuir-Blodgett technique. The computational modeling focuses on three key properties: pi-pi stacking interactions, molecular steric hindrance, and dynamic self-assembly orientation. This modeling guided the selection of a borazine molecular building block and enabled the successful experimental formation of a free-standing molecular-thin borazine-based film. Solely pi-pi stacking interactions were found to drive the formation of a bilayer film with a molecular thickness of 2.1 nm, capable of spanning 0.6 mu m diameter...Show moreBoron-nitride-rich organic thin materials based on borazines have gained significant attention for their potential in nano(opto)electronic and energy storage devices. We address synthetic challenges in producing effective borazine-based thin films by proposing a dual theoretical and experimental protocol. This combines a multiscale computational approach, using density functional theory and classical molecular dynamics, with synthesis and thin-film formation via the Langmuir-Blodgett technique. The computational modeling focuses on three key properties: pi-pi stacking interactions, molecular steric hindrance, and dynamic self-assembly orientation. This modeling guided the selection of a borazine molecular building block and enabled the successful experimental formation of a free-standing molecular-thin borazine-based film. Solely pi-pi stacking interactions were found to drive the formation of a bilayer film with a molecular thickness of 2.1 nm, capable of spanning 0.6 mu m diameter holes as a free-standing film. The agreement between theory and experiment confirms that the film retains essential features of the borazine molecular crystal, particularly intermolecular offset face-to-face pi-pi stacking and hexagonal-based pattern orientations. We thus establish a robust and transferable approach for modeling and synthesizing borazine-based thin materials, deepen the understanding of molecular interactions in borazine self-assembly, and demonstrate the suitability of the Langmuir-Blodgett technique for fabricating borazine-based 2D materials.Show less

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Computational modeling and self-assembly synthesis of borazine-based free-standing molecular-thin films