Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.
Chemistry. 2010 Jun 25;16(24):7143-63. doi: 10.1002/chem.201000621.
The reaction of U-shaped, bimetallic, Cu(I) complexes, assembled from a heteroditopic pincer, with cyano-capped pi-conjugated linkers gives a straightforward access to pi-stacked metallocyclophanes in good yields. In these assemblies, the pi-walls have an almost face-to-face arrangement. The versatility of this rational supramolecular synthesis is demonstrated with the use of linkers that have nanoscale lengths (up to 27.7 A), different chemical compositions (oligo(para-phenylenevinylene)s OPVs, oligo(phenylene)s, oligo(phenylethynylene)s), and alternative geometries (linear, angular). Linkers that incorporate an internal pyridyne moiety can also be employed. X-ray diffraction studies revealed that the metallocyclophanes based on linear linkers self-organize into infinite pi-stacked columns in the solid state with intermolecular distances of about 3.6 A. This approach, based on coordination-driven self-assembly, provides a novel and rational strategy for the stacking of extended pi-systems in the solid state.
U 型双金属 Cu(I) 配合物由杂双齿夹持配体组装而成，与氰基封端的π共轭连接体反应，以高收率直接得到π堆积金属环芳烃。在这些组装体中，π-壁几乎呈面对面排列。通过使用具有纳米级长度（长达 27.7 A）、不同化学组成（聚对苯乙炔 OPVs、聚亚苯基、聚亚苯乙炔）和替代几何形状（线性、角形）的连接体，证明了这种合理的超分子合成的多功能性。还可以使用包含内部吡啶基部分的连接体。X 射线衍射研究表明，基于线性连接体的金属环芳烃在固态中自组装成无限的π堆积柱，分子间距离约为 3.6 A。这种基于配位驱动自组装的方法为固态中扩展的π体系的堆积提供了一种新颖而合理的策略。
