Department of Chemistry and Pharmacy, Interdisciplinary Center of Molecular Materials (ICMM), Friedrich-Alexander-University of Erlangen-Nürnberg , Henkestrasse 42, 91054 Erlangen, Germany.
J Am Chem Soc. 2015 Mar 11;137(9):3308-17. doi: 10.1021/ja512048t. Epub 2015 Mar 3.
The first highly water-soluble perylene-calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π-π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficient water solubility at slightly basic conditions. The tetrahedrally shaped amphiphile displays an unprecedented aggregation behavior down to concentrations as low as 10(-7) mol L(-1). The intriguing self-assembly process of the compound in water as well as under changed polarity conditions, achieved by addition of THF, could be monitored by the complemented use of cryogenic transmission electron microscopy (cryo-TEM), UV-vis spectroscopy, and fluorescence spectroscopy. Molecular-dynamics and molecular modeling simulations helped in understanding the interplay of supramolecular and optical behavior.
首次提出了一种具有杯[4]芳烃支架作为结构确定中心平台的高水溶性苝酰亚胺混合体。在这种四面体形状的两亲性架构中，亲水性和疏水性亚单位位于杯芳烃平台的相反侧。疏水区包含两个苝二酰亚胺部分，这使得在自组装过程中能够产生强的π-π相互作用。两个亲水性的 Newkome 型树枝状分子提供了足够的水溶性，即使在稍碱性条件下也是如此。这种四面体形状的两亲分子在低至 10(-7)mol L(-1)的浓度下表现出前所未有的聚集行为。化合物在水中以及通过加入 THF 改变极性条件下的有趣自组装过程，可以通过补充使用低温透射电子显微镜（cryo-TEM）、紫外可见光谱和荧光光谱来监测。分子动力学和分子建模模拟有助于理解超分子和光学行为的相互作用。
