State Key Laboratory of Medicinal Chemical Biology, College of Pharmacy, Key Laboratory of Functional Polymer Materials of Ministry of Education, Nankai University, Tianjin, 300071, P. R. China.
School of Materials Science and Engineering, Nankai University, Tianjin, 300071, P. R. China.
Chemistry. 2020 Apr 6;26(20):4505-4509. doi: 10.1002/chem.202000462. Epub 2020 Mar 12.
Dye assemblies exhibit fascinating properties and performances, both of which depend critically on the mutual packing arrangement of dyes and on the supramolecular architecture. Herein, we engineered, for the first time, an intriguing chlorosome-mimetic 2D crystalline J-dimer lamellar structure based on halogenated dyes in aqueous media by employing two distinct orthogonal halogen-bonding (XB) interactions. As the only building motif, antiparallel J-dimer was formed and stabilized by single π-stacking and dual halogen⋅⋅⋅π interactions. With two substituted halogen atoms acting as XB donors and the other two acting as acceptors, the constituent J-dimer units were linked by quadruple highly-directional halogen⋅⋅⋅halogen interactions in a staggered manner, resulting in unique 2D lamellar dye assemblies. This work champions and advances halogen-bonding as a remarkably potent tool for engineering dye aggregates with a controlled molecular packing arrangement and supramolecular architecture.
染料组装体表现出迷人的性质和性能，这两者都取决于染料的相互堆积排列和超分子结构。在这里，我们首次通过在水相介质中利用两种不同的正交卤键（XB）相互作用，设计了一种基于卤化染料的有趣的类菌叶绿素模拟二维结晶 J-二聚体层状结构。作为唯一的构建基元，通过单个π堆积和双重卤化物···π相互作用形成并稳定了反平行 J-二聚体。由于两个取代的卤原子充当 XB 供体，另外两个充当受体，组成的 J-二聚体单元通过四重高度定向的卤化物···卤化物相互作用交错连接，形成独特的二维层状染料组装体。这项工作支持并推进了卤键作为一种非常有效的工具，用于工程化具有受控分子堆积排列和超分子结构的染料聚集体。
