Hierarchical Ordering in Adsorbed Overlayers of Chiral Tripod Molecules with Directional Interactions

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• 作者：Wojciech Rżysko ; Damian Nieckarz ; Paweł Szabelski
• 刊名：Journal of Physical Chemistry C
• 出版年：2017
• 出版时间：January 12, 2017
• 年：2017
• 卷：121
• 期：1
• 页码：410-420
• 全文大小：778K
• ISSN：1932-7455

文摘

Chiral molecules can adopt mirror-image configurations when adsorbed on solid substrates, and due to this unique property they can self-assemble into 2D mixed superstructures with complex geometries. In this contribution, we use the Monte Carlo simulation method to study the surface-confined organization of model chiral tripod molecules equipped with terminal centers providing directional short-range intermolecular interactions. These centers, representing functional groups, are the main source of chirality of the considered molecular units which are modeled as rigid planar structures comprising a few interconnected segments. Our simulations embrace enantiopure adsorbed systems, racemic overlayers, as well as nonracemic mixtures, and they are performed for two C₃-symmetric tectons differing in size. The obtained results, including structural and thermodynamic characteristics, demonstrate that the pattern formation in the modeled systems is highly sensitive to the composition of the adsorbed overlayer, leading to a cascade of coexisting phases with scalable properties. The insights from the theoretical investigations reported herein can be helpful in designing chiral functional surfaces with predefined architecture and functions. In particular, they hint at how to tune enantiomeric composition of adsorbed assemblies to create molecular patterns with different periodicities and porosities.