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In this study, a robust phosphine\u2010functionalized ultra\u2010microporous Cu(I\/II)\u2010organic framework, LIFM\u2010XYY\u201015, featuring open metal sites (OMSs) and rich aromatic pore walls, is designed to enable one\u2010step CH\n                    <jats:sub>4<\/jats:sub>\n                    purification from a quaternary C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    \/C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    \/CO\n                    <jats:sub>2<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    mixture. Notably, LIFM\u2010XYY\u201015 exhibits much higher C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    \/C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    \/CO\n                    <jats:sub>2<\/jats:sub>\n                    uptakes than CH\n                    <jats:sub>4<\/jats:sub>\n                    , showing C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    , C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    , and CO\n                    <jats:sub>2<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    uptake ratios of 2.46, 2.30, and 3.92 at 298 K and 1\u00a0bar, respectively, which are significantly raised to 12.18, 8.59, and 9.89 at 0.1\u00a0bar. The separation potentials (\u2206\n                    <jats:italic>q<\/jats:italic>\n                    ) reach 22.12 (C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    ), 20.34 (C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    ), and 43.69 (CO\n                    <jats:sub>2<\/jats:sub>\n                    \/CH\n                    <jats:sub>4<\/jats:sub>\n                    ) cm\n                    <jats:sup>3<\/jats:sup>\n                    cm\n                    <jats:sup>\u22123<\/jats:sup>\n                    at 298 K and 1\u00a0bar, demonstrating excellent CH\n                    <jats:sub>4<\/jats:sub>\n                    purification ability from the quaternary mixture. Breakthrough experiments confirm the delivery of high\u2010purity CH\n                    <jats:sub>4<\/jats:sub>\n                    (\u226599.9%) with a productivity of 1.39\u00a0mol L\n                    <jats:sup>\u22121<\/jats:sup>\n                    with excellent recyclability. The in situ single\u2010crystal x\u2010ray diffraction (SCXRD), in situ FT\u2010IR spectroscopy, and molecular simulations reveal that the exceptional selectivity arises from the synergistic interplay of agostic\u2010type C\u2500H\u00b7\u00b7\u00b7Cu, quadrupole\u2010electrostatic Cu\u00b7\u00b7\u00b7\u2010CO\n                    <jats:sub>2<\/jats:sub>\n                    , and alkane C\u2500H\u00b7\u00b7\u00b7O\/\u03c0 interactions, which collectively reinforce the affinity for C\n                    <jats:sub>2<\/jats:sub>\n                    \u2013C\n                    <jats:sub>3<\/jats:sub>\n                    hydrocarbons and CO\n                    <jats:sub>2<\/jats:sub>\n                    while disfavoring CH\n                    <jats:sub>4<\/jats:sub>\n                    . This work discloses a crucial role of agostic\u2010type interactions as a powerful yet underexplored design principle for selective hydrocarbon separations.\n                  <\/jats:p>","DOI":"10.1002\/anie.2462968","type":"journal-article","created":{"date-parts":[[2026,10,11]],"date-time":"2026-10-11T02:38:18Z","timestamp":1791686298000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Cooperative Agostic\u2010Type C\u2500H\u00b7\u00b7\u00b7Cu, Quadrupolar Cu\u00b7\u00b7\u00b7CO\n                    <sub>2<\/sub>\n                    , and C\u2500H\u00b7\u00b7\u00b7O\/\u03c0 Interactions in an Ultra\u2010Microporous MOF Enable One\u2010Step Methane Purification From Quaternary C\n                    <sub>3<\/sub>\n                    H\n                    <sub>8<\/sub>\n                    \/C\n                    <sub>2<\/sub>\n                    H\n                    <sub>6<\/sub>\n                    \/CO\n                    <sub>2<\/sub>\n                    \/CH\n                    <sub>4<\/sub>"],"prefix":"10.1002","author":[{"given":"Qing\u2010Hua","family":"Dai","sequence":"first","affiliation":[{"name":"GBRCE For Functional Molecular Engineering Lehn Institute of Functional Materials IGCME School of Chemistry Sun Yat\u2010Sen University  Guangzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yang\u2010Yang","family":"Xiong","sequence":"additional","affiliation":[{"name":"GBRCE For Functional Molecular Engineering Lehn Institute of Functional Materials IGCME School of Chemistry Sun Yat\u2010Sen University  Guangzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei","family":"Zeng","sequence":"additional","affiliation":[{"name":"GBRCE For Functional Molecular Engineering Lehn Institute of Functional Materials IGCME School of Chemistry Sun Yat\u2010Sen University  Guangzhou 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