Department of Physical Chemistry and Applied Thermodynamics, University of Córdoba, Córdoba, Spain.
Langmuir. 2012 Aug 21;28(33):12114-21. doi: 10.1021/la302440g. Epub 2012 Aug 10.
The design of new molecules with directed interactions to functional molecules as complementary building blocks is one of the main goals of supramolecular chemistry. A new p-tert-butylcalix[6]arene monosubstituted derivative bearing only one alkyl chain with an acid group (C6A3C) has been synthesized. The C6A3C has been successfully used for building Langmuir monolayers at the air-water interface. The C6A3C molecule adopts a flatlike orientation with respect to the air-water interface. The molecular structure gives the molecule amphiphilic character, while allowing the control of both the dissociation degree and the molecular conformation at the air-water interface. The C63AC has been combined with pristine fullerene (C60) to form the supramolecular complex C6A3C:C60 in 2:1 molar ratio (CFC). The CFC complex retains the ability of C6A3C to form Langmuir monolayers at the air/water interface. The interfacial molecular arrangement of the CFC complex has been convincingly described by in situ UV-vis reflection spectroscopy and synchrotron X-ray reflectivity measurements. Computer simulations complement the experimental data, confirming a perpendicular orientation of the calixarene units of CFC with respect to the air-water interface. This orientation is stabilized by the formation of intermolecular H-bonds. The interfacial monolayer of the CFC supramolecular complex is proposed as a useful model for the well-defined self-assembly of recognition and functional building blocks.
设计具有定向相互作用的新分子，将其作为功能分子的互补构建块，是超分子化学的主要目标之一。我们已经合成了一种新型的 p-叔丁基杯[6]芳烃单取代衍生物，该衍生物仅带有一个带有酸性基团的烷基链（C6A3C）。C6A3C 已成功用于在气/水界面上构建 Langmuir 单分子层。C6A3C 分子相对于气/水界面呈平面取向。分子结构赋予分子两亲性特征，同时允许控制气/水界面处的离解度和分子构象。C63AC 与原始富勒烯（C60）结合，形成摩尔比为 2:1 的超分子复合物 C6A3C:C60（CFC）。CFC 复合物保留了 C6A3C 在气/水界面上形成 Langmuir 单分子层的能力。通过原位紫外可见反射光谱和同步辐射 X 射线反射率测量，令人信服地描述了 CFC 复合物的界面分子排列。计算机模拟补充了实验数据，证实了 CFC 中环糊精单元相对于气/水界面的垂直取向。这种取向通过形成分子间氢键得到稳定。CFC 超分子复合物的界面单层被提议作为用于定义明确的识别和功能构建块自组装的有用模型。
