The codriven assembly of molecular metalla-links (613, 623) and metalla-knots (41, 31) via coordination and noncovalent interactions

作者：Shu‐Jin Bao, Yan Zou, Haining Zhang, Guo‐Xin Jin · 发表于：Proceedings of the National Academy of Sciences · 年份：2024 · DOI：10.1073/pnas.2407570121 · 被引用次数：41 · 研究领域：Supramolecular Chemistry and Complexes、Supramolecular Self-Assembly in Materials、Crystallography and molecular interactions

Although mechanically interlocked molecules (MIMs) display unique properties and functions associated with their intricate connectivity, limited assembly strategies are available for their synthesis. Herein, we presented a synergistic assembly strategy based on coordination and noncovalent interactions (π–π stacking and CH⋯π interactions) to selectively synthesize molecular closed three-link chains ( 6 1 3 links), highly entangled figure-eight knots ( 4 1 knots), trefoil knot ( 3 1 knot), and Borromean ring ( 6 2 3 link). 6 1 3 links can be created by the strategic assembly of nonlinear multicurved ligands incorporating a furan or phenyl group with the long binuclear half-sandwich organometallic Cp*Rh III (Cp* = η 5 -pentamethylcyclopentadienyl) clip. However, utilizing much shorter binuclear Cp*Rh III units for union with the 2,6-naphthyl-containing ligand led to a 4 1 knot because of the increased π–π stacking interactions between four consecutive stacked layers and CH⋯π interactions. Weakening such π–π stacking interactions resulted in a 3 1 knot. The universality of this synergistic assembly strategy for building 4 1 knots was verified by utilizing a 1,5-naphthyl-containing ligand. Quantitative conversion between the 4 1 knot and the simple macrocycle species was accomplished by adjusting the concentrations monitored by NMR spectroscopy and electro...