{\pi}-{\pi} Interaction-facilitated formation of interwoven trimeric cage-catenanes with topological chirality

Abstract

Catenanes as interlocked molecules with a nonplanar graph have gained increasing attention for their unique features such as topological chirality. To date, the majority of research in this field has been focusing on catenanes comprising monocyclic rings. Due to the lack of rational synthetic strategy, catenanes of cage-like monomers are hardly accessible. Here we report on the construction of an interwoven trimeric catenane that is composed of achiral organic cages, which exhibits topological chirality. Our rational design begins with a pure mathematical analysis, revealing that the formation probability of the interwoven trimeric catenane surpasses that of its chain-like analogue by 20%; while driven by efficient template effect provided by strong {\pi}-{\pi} stacking of aromatic panels, the interwoven structure emerges as the dominant species, almost ruling out the formation of the chain-like isomer. Its topological chirality is unambiguously unravelled by chiral-HPLC, CD spectroscopy and X-ray diffraction. Our probability analysis-aided rational design strategy would pave a new venue for the efficient synthesis of topologically sophisticated structures in one pot.