An “All-in-One” Synthetic Strategy for Linear Metalla[4]Catenanes
Ye Lu, Dong Liu, Yue‐Jian Lin, Zhen Hua Li, F. Ekkehardt Hahn, Guo‐Xin Jin
Abstract
One fascinating and challenging synthetic target in the field of mechanically interlocked molecules is the family of linear [4]catenanes, which are topologically identical to the logo of automobile maker Audi. Herein, we report an “all-in-one” synthetic strategy for the synthesis of linear metalla[n]catenanes (n = 2–4) by the coordination-driven self-assembly of Cp*Rh-based (Cp* = η5-pentamethylcyclopentadienyl) organometallic rectangle π-donors and tetracationic organic cyclophane π-acceptors. We selected the pyrenyl group as the π-donor unit, leading to homogeneous metalla[2]catenanes and cyclic metalla[3]catenanes via π-stacking interactions. By taking advantage of the strong electrostatic interactions between π-donor units and π-acceptor units, a heterogeneous metalla[2]catenanes and linear metalla[3]catenanes, respectively, could be obtained by the simple stirring of homogeneous metalla[2]catenanes with a suitable tetracationic cyclophane. On this basis, this “all-in-one” synthetic strategy was further used to realize a quantitative one-step synthesis of a linear metalla[4]catenanes via the self-assembly of cyclic metalla[3]catenanes and tetracationic cyclophanes. All heterogeneous metalla[n]catenanes (n = 2–4) were fully characterized by single-crystal X-ray analysis, NMR spectroscopy and electrospray ionization mass spectrometry.