Concentration-Dependent Supramolecular Engineering of Hydrogen-Bonded Nanostructures at Surfaces: Predicting Self-Assembly in 2D
Concentration-Dependent Supramolecular Engineering of Hydrogen-Bonded Nanostructures at Surfaces: Predicting Self-Assembly in 2D
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DOI：
10.1021/ja4002025
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发表时间：
2013-05-08
影响因子：
15
通讯作者：
Samori, Paolo
中科院分区：
文献类型：
--
作者：
Ciesielski, Artur;Szabelski, Pawel J.;Samori, Paolo
我们报告了一个联合的计算和实验研究的浓度依赖性的自组装的平面C-3对称分子在表面。作为一个模型系统，我们选择了一个刚性的分子模块，1，3，5-三（吡啶-4-基乙炔基）苯，它可以通过氢键（H-键）进行自缔合，形成有序的二维纳米结构。特别是，晶格Monte Carlo方法，结合密度泛函计算，探讨了这种三脚架形分子的自发超分子组织下的表面限制。我们分析了不同弱氢键模式的稳定性以及起始分子浓度对二维超分子堆积的影响。我们发现，有序的，密集的单层和二维多孔网络，分别在高和低浓度。在石墨-溶液界面的分子自组装的浓度依赖的扫描隧道显微镜调查显示超分子图案，这是在完美的协议与通过模拟得到的。因此，我们的计算方法代表了一个确定性的预测在表面和界面的分子自组装前进了一步。
We report a joint computational and experimental study on the concentration-dependent self-assembly of a flat C-3-symmetric molecule at surfaces. As a model system we have chosen a rigid molecular module, 1,3,5-tris(pyridine-4-ylethynyl)benzene, which can undergo self-association via hydrogen bonding (H-bonding) to form ordered 2D nanostructures. In particular, the lattice Monte Carlo method, combined with density functional calculations, was employed to explore the spontaneous supramolecular organization of this tripod-shaped molecule under surface confinement. We analyzed the stability of different weak H-bonded patterns and the influence of the concentration of the starting molecule on the 2D supramolecular packing. We found that ordered, densely packed monolayers and 2D porous networks are obtained at high and low concentrations, respectively. A concentration-dependent scanning tunneling microscopy investigation of the molecular self-assembly at a graphite-solution interface revealed supramolecular motifs, which are in perfect agreement with those obtained by simulations. Therefore, our computational approach represents a step forward toward the deterministic prediction of molecular self-assembly at surfaces and interfaces.