{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Bao SJ"],"funding":["National Natural Foundation of China"],"pagination":["e2407570121"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC11228484"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["121(27)"],"pubmed_abstract":["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 ([Formula: see text] links), highly entangled figure-eight knots ([Formula: see text] knots), trefoil knot ([Formula: see text] knot), and Borromean ring ([Formula: see text] link). [Formula: see text] 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<sup>III</sup> (Cp* = <i>η</i><sup>5</sup>-pentamethylcyclopentadienyl) clip. However, utilizing much shorter binuclear Cp*Rh<sup>III</sup> units for union with the 2,6-naphthyl-containing ligand led to a [Formula: see text] 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 [Formula: see text] knot. The universality of this synergistic assembly strategy for building [Formula: see text] knots was verified by utilizing a 1,5-naphthyl-containing ligand. Quantitative conversion between the [Formula: see text] knot and the simple macrocycle species was accomplished by adjusting the concentrations monitored by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing the stiff π-conjugated area of the binuclear unit afforded molecular Borromean ring, and this topology is a topological isomer of the [Formula: see text] link. These artificial metalla-links and metalla-knots were confirmed by single-crystal X-ray diffraction, NMR and ESI-MS. The results offer a potent strategy for building higher-order MIMs and emphasize the critical role that noncovalent interactions play in creating sophisticated topologies."],"journal":["Proceedings of the National Academy of Sciences of the United States of America"],"pubmed_title":["The codriven assembly of molecular metalla-links ([Formula: see text], [Formula: see text]) and metalla-knots ([Formula: see text], [Formula: see text]) via coordination and noncovalent interactions."],"pmcid":["PMC11228484"],"funding_grant_id":["22031003 21720102004"],"pubmed_authors":["Zou Y","Jin GX","Bao SJ","Zhang HN"],"additional_accession":[]},"is_claimable":false,"name":"The codriven assembly of molecular metalla-links ([Formula: see text], [Formula: see text]) and metalla-knots ([Formula: see text], [Formula: see text]) via coordination and noncovalent interactions.","description":"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 ([Formula: see text] links), highly entangled figure-eight knots ([Formula: see text] knots), trefoil knot ([Formula: see text] knot), and Borromean ring ([Formula: see text] link). [Formula: see text] 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<sup>III</sup> (Cp* = <i>η</i><sup>5</sup>-pentamethylcyclopentadienyl) clip. However, utilizing much shorter binuclear Cp*Rh<sup>III</sup> units for union with the 2,6-naphthyl-containing ligand led to a [Formula: see text] 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 [Formula: see text] knot. The universality of this synergistic assembly strategy for building [Formula: see text] knots was verified by utilizing a 1,5-naphthyl-containing ligand. Quantitative conversion between the [Formula: see text] knot and the simple macrocycle species was accomplished by adjusting the concentrations monitored by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing the stiff π-conjugated area of the binuclear unit afforded molecular Borromean ring, and this topology is a topological isomer of the [Formula: see text] link. These artificial metalla-links and metalla-knots were confirmed by single-crystal X-ray diffraction, NMR and ESI-MS. The results offer a potent strategy for building higher-order MIMs and emphasize the critical role that noncovalent interactions play in creating sophisticated topologies.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Jul","modification":"2025-04-18T21:59:25.176Z","creation":"2025-04-07T09:52:20.923Z"},"accession":"S-EPMC11228484","cross_references":{"pubmed":["38941275"],"doi":["10.1073/pnas.2407570121"]}}