{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T14:11:20Z","timestamp":1790604680134,"version":"4.1.0"},"reference-count":44,"publisher":"American Chemical Society (ACS)","issue":"38","license":[{"start":{"date-parts":[[2026,9,13]],"date-time":"2026-09-13T00:00:00Z","timestamp":1789257600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,13]],"date-time":"2026-09-13T00:00:00Z","timestamp":1789257600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,13]],"date-time":"2026-09-13T00:00:00Z","timestamp":1789257600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100018546","name":"Postdoctoral Innovation Project of Shandong Province","doi-asserted-by":"publisher","award":["SDCX-ZG-202603056"],"award-info":[{"award-number":["SDCX-ZG-202603056"]}],"id":[{"id":"10.13039\/501100018546","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22072077"],"award-info":[{"award-number":["22072077"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100007129","name":"Natural Science Foundation of Shandong Province","doi-asserted-by":"publisher","award":["ZR2023YQ019"],"award-info":[{"award-number":["ZR2023YQ019"]}],"id":[{"id":"10.13039\/501100007129","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Shandong Provincial Center for Fundamental Science Research","award":["YDZX2024150"],"award-info":[{"award-number":["YDZX2024150"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,28]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The design of robust heterogeneous catalysts that rival the performance of homogeneous systems remains a fundamental challenge. Herein, we report a hydrazone-linked covalent organic framework (DHPy-COF) engineered as a cooperative macromolecular ligand with preorganized (O,N,O)-tridentate chelation sites for Cu(II) immobilization, a coordination mode unequivocally validated by single-crystal X-ray diffraction of a salicylhydrazone model complex. The resulting Cu(II)@DHPy-COF efficiently catalyzes Chan\u2013Lam coupling of arylboronic acids with diverse N-nucleophiles under ambient conditions (up to 98% yield) and exhibits exceptional recyclability over five cycles with negligible Cu leaching (&amp;lt;0.2%). A control study employing an OH-free analogue unequivocally demonstrates that the ortho-phenolic hydroxyl group is functionally essential for cooperative chelation and sustained catalytic stability. This work establishes a paradigm shift, from employing COFs as inert supports to using them as functional ligands, offering a generalizable strategy for robust heterogeneous catalysis.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c04497","type":"journal-article","created":{"date-parts":[[2026,9,13]],"date-time":"2026-09-13T18:01:17Z","timestamp":1789322477000},"page":"22828-22836","source":"Crossref","is-referenced-by-count":0,"title":["Engineering\na Hydrazone-Linked Covalent Organic Framework\nas a Cooperative Macromolecular Ligand for Recyclable Cu-Catalyzed\nChan\u2013Lam Coupling"],"prefix":"10.1021","volume":"65","author":[{"given":"Fei","family":"Li","sequence":"first","affiliation":[{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]},{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dao-Zheng","family":"Wang","sequence":"additional","affiliation":[{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yue-Hua","family":"Liu","sequence":"additional","affiliation":[{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiang","family":"Wang","sequence":"additional","affiliation":[{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5186-340X","authenticated-orcid":true,"given":"Yan","family":"Geng","sequence":"additional","affiliation":[{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8165-5871","authenticated-orcid":true,"given":"Bing-Jian","family":"Yao","sequence":"additional","affiliation":[{"name":"Shandong Normal University , , ,","place":["Jinan, P. R. China, 250014"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,13]]},"reference":[{"issue":"24","key":"2026092809223783800_cit1","doi-asserted-by":"publisher","first-page":"9283","DOI":"10.1039\/c3cs60228a","article-title":"C\u2013N bond forming cross-coupling reactions: an\noverview","volume":"42","author":"Bariwal","year":"2013","journal-title":"Chem. Soc. Rev."},{"issue":"5","key":"2026092809223783800_cit2","doi-asserted-by":"publisher","first-page":"1257","DOI":"10.1039\/C5CS00534E","article-title":"Transition-metal catalysed C\u2013N\nbond activation","volume":"45","author":"Wang","year":"2016","journal-title":"Chem. Soc. Rev."},{"issue":"19","key":"2026092809223783800_cit3","doi-asserted-by":"publisher","first-page":"12564","DOI":"10.1021\/acs.chemrev.6b00512","article-title":"Applications of\npalladium-catalyzed C\u2013N cross-coupling\nreactions","volume":"116","author":"Ruiz-Castillo","year":"2016","journal-title":"Chem. Rev."},{"issue":"27","key":"2026092809223783800_cit4","doi-asserted-by":"publisher","first-page":"18715","DOI":"10.1039\/D2RA07412E","article-title":"Applications\nof palladium-catalyzed\nC\u2013N cross-coupling reactions in pharmaceutical compounds","volume":"13","author":"Emadi","year":"2023","journal-title":"RSC Adv."},{"issue":"29","key":"2026092809223783800_cit5","doi-asserted-by":"publisher","first-page":"25527","DOI":"10.1021\/jacs.5c05884","article-title":"Enantioconvergent Chan\u2013Lam coupling: synthesis of chiral benzylic\namides via Cu-catalyzed deborylative amidation","volume":"147","author":"Vu","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"1","key":"2026092809223783800_cit6","doi-asserted-by":"publisher","first-page":"4747","DOI":"10.1038\/s41467-024-49089-0","article-title":"A combined experimental and computational\nstudy of ligand-controlled Chan\u2013Lam coupling of sulfenamides","volume":"15","author":"Han","year":"2024","journal-title":"Nat. Commun."},{"issue":"9","key":"2026092809223783800_cit7","doi-asserted-by":"publisher","first-page":"2320","DOI":"10.1039\/D4CY00034J","article-title":"Recent advances\nin Chan\u2013Lam\ncoupling reaction","volume":"14","author":"Devi","year":"2024","journal-title":"Catal. Sci. Technol."},{"issue":"16","key":"2026092809223783800_cit8","doi-asserted-by":"publisher","first-page":"3311","DOI":"10.1002\/adsc.202000495","article-title":"A review\non the latest progress of\nChan\u2013Lam coupling reaction","volume":"362","author":"Chen","year":"2020","journal-title":"Adv. Synth.\nCatal."},{"issue":"16","key":"2026092809223783800_cit9","doi-asserted-by":"publisher","first-page":"2830","DOI":"10.1021\/acs.orglett.3c00779","article-title":"Sulfur-arylation of sulfenamides via Chan\u2013Lam\ncoupling with boronic acids: access to high oxidation state sulfur\npharmacophores","volume":"25","author":"Greenwood","year":"2023","journal-title":"Org. Lett."},{"issue":"1","key":"2026092809223783800_cit10","doi-asserted-by":"publisher","first-page":"9121","DOI":"10.1038\/s41467-025-64155-x","article-title":"Overcoming limitations in Chan\u2013Lam\namination with alkylboronic esters via aminyl radical substitution","volume":"16","author":"Xiao","year":"2025","journal-title":"Nat. Commun."},{"issue":"2","key":"2026092809223783800_cit11","doi-asserted-by":"publisher","first-page":"338","DOI":"10.1021\/ol403717f","article-title":"Copper-catalyzed Chan\u2013Lam\ncoupling between sulfonyl azides and boronic acids at room temperature","volume":"16","author":"Moon","year":"2014","journal-title":"Org. Lett."},{"issue":"4","key":"2026092809223783800_cit12","doi-asserted-by":"publisher","first-page":"847","DOI":"10.1039\/D3SU00093A","article-title":"Cu-catalysed\nChan\u2013Evans\u2013Lam reaction meets deep eutectic solvents:\nefficient and selective C\u2013N bond formation under aerobic conditions\nat room temperature","volume":"1","author":"Cicco","year":"2023","journal-title":"RSC Sustainability"},{"issue":"3","key":"2026092809223783800_cit13","doi-asserted-by":"publisher","first-page":"1856","DOI":"10.1021\/jo502828r","article-title":"A synthetic approach\nto N-aryl carbamates via copper-catalyzed Chan\u2013Lam\ncoupling at room temperature","volume":"80","author":"Moon","year":"2015","journal-title":"J. Org. Chem."},{"issue":"16","key":"2026092809223783800_cit14","doi-asserted-by":"publisher","first-page":"4251","DOI":"10.1039\/D0SC00623H","article-title":"An isocyanide ligand for the rapid\nquenching and efficient removal of copper residues after Cu\/TEMPO-catalyzed\naerobic alcohol oxidation and atom transfer radical polymerization","volume":"11","author":"Szczepaniak","year":"2020","journal-title":"Chem. Sci."},{"issue":"9","key":"2026092809223783800_cit15","doi-asserted-by":"publisher","first-page":"7289","DOI":"10.1021\/acscatal.4c01006","article-title":"Recycling of homogeneous\ncatalysts-basic principles, industrial practice, and guidelines for\nexperiments and evaluation","volume":"14","author":"Fassbach","year":"2024","journal-title":"ACS Catal."},{"issue":"1","key":"2026092809223783800_cit16","doi-asserted-by":"publisher","first-page":"3","DOI":"10.1002\/adsc.201500846","article-title":"Why does industry\nnot use immobilized\ntransition metal complexes as catalysts?","volume":"358","author":"Hu\u0308bner","year":"2016","journal-title":"Adv.\nSynth. Catal."},{"issue":"1","key":"2026092809223783800_cit17","doi-asserted-by":"publisher","first-page":"34495","DOI":"10.1038\/s41598-025-14653-1","article-title":"Design and catalytic\nperformance of a novel two-dimensional copper metal-organic framework\nfor green synthesis of tetrahydrobenzo[b]pyrans","volume":"15","author":"Bahaderani","year":"2025","journal-title":"Sci. Rep."},{"key":"2026092809223783800_cit18","doi-asserted-by":"publisher","first-page":"116","DOI":"10.1016\/j.micromeso.2017.06.020","article-title":"Zeolite supported palladium catalysts\nfor hydroalkylation of phenolic model compounds","volume":"252","author":"Akhmetzyanova","year":"2017","journal-title":"Microporous Mesoporous Mater."},{"issue":"12","key":"2026092809223783800_cit19","doi-asserted-by":"publisher","first-page":"17718","DOI":"10.1021\/acsami.3c14808","article-title":"Ruthenium-picolylamine-incorporated mixed-linker MOFs:\nhighly active heterogeneous catalysts for olefin and aldehyde hydrogenation","volume":"17","author":"Almeida","year":"2025","journal-title":"ACS Appl. Mater. Interfaces"},{"issue":"11","key":"2026092809223783800_cit20","doi-asserted-by":"publisher","first-page":"9072","DOI":"10.1039\/C5RA26432D","article-title":"Facile, low-cost, and\nscalable fabrication of particle size and pore\nstructure tuneable monodisperse mesoporous silica nanospheres as supports\nfor advanced solid acid catalysts","volume":"6","author":"Zhao","year":"2016","journal-title":"RSC Adv."},{"key":"2026092809223783800_cit21","doi-asserted-by":"publisher","first-page":"99","DOI":"10.1016\/j.ccr.2015.12.005","article-title":"Metal nanoparticles\nsupported on two-dimensional graphenes as heterogeneous catalysts","volume":"312","author":"Navalon","year":"2016","journal-title":"Coord. Chem. Rev."},{"issue":"40","key":"2026092809223783800_cit22","doi-asserted-by":"publisher","first-page":"8958","DOI":"10.1039\/C9OB01946D","article-title":"Cercosporin-photocatalyzed sp3 (C\u2013H) activation for the synthesis of pyrrolo[3,4-c]quinolones","volume":"17","author":"Li","year":"2019","journal-title":"Org. Biomol. Chem."},{"issue":"28","key":"2026092809223783800_cit23","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202405769","article-title":"Crystalline olefin-linked chiral\ncovalent organic frameworks as a platform for asymmetric catalysis","volume":"63","author":"He","year":"2024","journal-title":"Angew. Chem., Int. Ed."},{"issue":"18","key":"2026092809223783800_cit24","doi-asserted-by":"publisher","first-page":"9619","DOI":"10.1039\/D4GC03467H","article-title":"Covalent organic frameworks\nas heterogeneous photocatalysts for cross-coupling reactions","volume":"26","author":"Chakraborty","year":"2024","journal-title":"Green Chem."},{"issue":"14","key":"2026092809223783800_cit25","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202318180","article-title":"Post-synthetic rhodium\n(III) complexes in covalent organic frameworks for photothermal heterogeneous\nC\u2013H activation","volume":"63","author":"Li","year":"2024","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026092809223783800_cit26","doi-asserted-by":"publisher","first-page":"217201","DOI":"10.1016\/j.ccr.2025.217201","article-title":"Polyoxometalate-based\ncovalent organic\nframeworks: The next generation of heterogeneous catalysts","volume":"548","author":"Ebrahimi","year":"2026","journal-title":"Coord. Chem. Rev."},{"issue":"1","key":"2026092809223783800_cit27","doi-asserted-by":"publisher","first-page":"1267","DOI":"10.1038\/s41467-024-45457-y","article-title":"Robust links\nin photoactive covalent organic frameworks enable effective photocatalytic\nreactions under harsh conditions","volume":"15","author":"Wang","year":"2024","journal-title":"Nat. Commun."},{"issue":"35","key":"2026092809223783800_cit28","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202505329","article-title":"PyBOX-integrated\nchiral covalent organic frameworks","volume":"64","author":"Li","year":"2025","journal-title":"Angew. Chem.,\nInt. Ed."},{"key":"2026092809223783800_cit29","doi-asserted-by":"publisher","first-page":"126251","DOI":"10.1016\/j.apcatb.2025.126251","article-title":"Unraveling the effect\nof \u03c0\u2013\u03c0 interactions on heterocyclic-linked\ncovalent organic frameworks for photocatalytic pollutants degradation","volume":"385","author":"Luo","year":"2026","journal-title":"Appl. Catal. B"},{"issue":"12","key":"2026092809223783800_cit30","doi-asserted-by":"publisher","first-page":"10144","DOI":"10.1021\/acscatal.5c01328","article-title":"Tuning linkage and dimensionality in covalent organic frameworks\nfor enhanced photocatalytic hydrogen peroxide production","volume":"15","author":"Liao","year":"2025","journal-title":"ACS Catal."},{"key":"2026092809223783800_cit31","doi-asserted-by":"publisher","first-page":"142","DOI":"10.1016\/S1872-2067(24)60184-1","article-title":"Recent advances of covalent organic\nframeworks-based photocatalysts:\nprinciples, designs, and applications","volume":"70","author":"Dong","year":"2025","journal-title":"Chin.\nJ. Catal."},{"issue":"8","key":"2026092809223783800_cit32","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202522928","article-title":"Chiral phosphoric\nacid\u2013functionalized three-dimensional covalent organic frameworks\nwith exceptional chemical stability for asymmetric catalysis","volume":"65","author":"Li","year":"2026","journal-title":"Angew. Chem., Int. Ed."},{"issue":"3","key":"2026092809223783800_cit33","doi-asserted-by":"publisher","first-page":"102334","DOI":"10.1016\/j.chempr.2024.10.001","article-title":"Modulating hetero-multimetallic atoms\nin covalent organic frameworks for efficient oxidization of olefin\ncompounds","volume":"11","author":"Meng","year":"2025","journal-title":"Chem"},{"issue":"86","key":"2026092809223783800_cit34","doi-asserted-by":"publisher","first-page":"16806","DOI":"10.1039\/D5CC04684J","article-title":"Cobalt-\nand ionic liquid-functionalized covalent organic framework for cooperative\ncatalytic CO2 cycloaddition","volume":"61","author":"Li","year":"2025","journal-title":"Chem.\nCommun."},{"issue":"5","key":"2026092809223783800_cit35","doi-asserted-by":"publisher","first-page":"3044","DOI":"10.1021\/acscatal.2c05442","article-title":"Low oxidation\nstate cobalt center stabilized by a covalent organic framework to\npromote hydroboration of olefins","volume":"13","author":"Gutierrez","year":"2023","journal-title":"ACS Catal."},{"issue":"16","key":"2026092809223783800_cit36","doi-asserted-by":"publisher","first-page":"3298","DOI":"10.1039\/D3QM00188A","article-title":"Covalent organic frameworks\nin heterogeneous\ncatalysis: recent advances and future perspective","volume":"7","author":"Alsudairy","year":"2023","journal-title":"Mater. Chem. Front."},{"issue":"37","key":"2026092809223783800_cit37","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202511024","article-title":"Electron\/proton transport engineering in acylhydrazone-linked covalent\norganic framework for efficient solar-driven H2O2 production","volume":"64","author":"Ma","year":"2025","journal-title":"Angew. Chem., Int. Ed."},{"issue":"10","key":"2026092809223783800_cit38","doi-asserted-by":"publisher","first-page":"4932","DOI":"10.1021\/jacs.0c00553","article-title":"Scalable construction\nof highly crystalline acylhydrazone\ntwo-dimensional covalent organic frameworks via dipole-induced antiparallel\nstacking","volume":"142","author":"Li","year":"2020","journal-title":"J. Am. Chem. Soc."},{"issue":"10","key":"2026092809223783800_cit39","doi-asserted-by":"publisher","first-page":"10945","DOI":"10.1021\/jacs.5c21545","article-title":"Conjugation\nlock-in reinforced sulfur-heteropolycyclic covalent organic frameworks\nwith asymmetric electron distribution for photocatalytic aerobic oxidation\nreactions","volume":"148","author":"Yang","year":"2026","journal-title":"J. Am. Chem. Soc."},{"issue":"19","key":"2026092809223783800_cit40","doi-asserted-by":"publisher","first-page":"5641","DOI":"10.1002\/anie.201500400","article-title":"Narcissistic\nself-sorting in self-assembled\ncages of rare earth metals and rigid ligands","volume":"54","author":"Johnson","year":"2015","journal-title":"Angew. Chem., Int. Ed."},{"issue":"5","key":"2026092809223783800_cit41","doi-asserted-by":"publisher","first-page":"3393","DOI":"10.1021\/acs.inorgchem.0c03783","article-title":"Gram-scale synthesis of Cu(II)@COF via solid-state\ncoordination approach for catalysis of alkyne-dihalomethane-amine\ncoupling","volume":"60","author":"Kan","year":"2021","journal-title":"Inorg. Chem."},{"issue":"87","key":"2026092809223783800_cit42","doi-asserted-by":"publisher","first-page":"17029","DOI":"10.1039\/D5CC04282H","article-title":"Chiral pool-engineered\nhomochiral covalent organic\nframeworks for catalytic asymmetric synthesis of drug intermediate","volume":"61","author":"Li","year":"2025","journal-title":"Chem. Commun."},{"issue":"25","key":"2026092809223783800_cit43","doi-asserted-by":"publisher","first-page":"11531","DOI":"10.1021\/acs.inorgchem.4c00416","article-title":"Computational assessment of the mechanistic\njourney in Chan\u2013Lam-based arylation of imidazoles","volume":"63","author":"Khilari","year":"2024","journal-title":"Inorg. Chem."},{"issue":"18","key":"2026092809223783800_cit44","doi-asserted-by":"publisher","first-page":"6219","DOI":"10.1021\/acs.joc.5c00283","article-title":"CuF2\/DTBP-catalyzed Chan\u2013Lam coupling of oxazolidinones with arylboronic\nacid pinacol ester: scope and application","volume":"90","author":"Roy","year":"2025","journal-title":"J.\nOrg. Chem."}],"container-title":["Inorganic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.inorgchem.6c04497","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/65\/38\/22828\/68493483\/acs.inorgchem.6c04497.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/65\/38\/22828\/68493483\/acs.inorgchem.6c04497.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T13:38:32Z","timestamp":1790602712000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/inocaj\/article\/65\/38\/22828\/5428995\/Engineering-a-Hydrazone-Linked-Covalent-Organic"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,13]]},"references-count":44,"journal-issue":{"issue":"38","published-online":{"date-parts":[[2026,9,13]]},"published-print":{"date-parts":[[2026,9,28]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.inorgchem.6c04497","relation":{},"ISSN":["0020-1669","1520-510X"],"issn-type":[{"value":"0020-1669","type":"print"},{"value":"1520-510X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,13]]}}}