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The transition-metal phosphorus trichalcogenide MnPSe3 has been theoretically predicted to host an intrinsic ferromagnetic half-metallic state in its monolayer under sufficient carrier doping. However, realizing experimentally accessible half-metallicity in this system poses a great challenge, as the controversy over the magnetic state of organic-ion-intercalated MnPSe3 crystals, which are commonly regarded as doped monolayers, remains unresolved. Here, we resolve this controversy by identifying a canted antiferromagnetic ground state in pyrrolidinium-intercalated MnPSe3, which originates from the combined effects of competition between direct Mn\u2013Mn antiferromagnetic exchange and Mn\u2013Se\u2013Mn ferromagnetic superexchange, as well as enhanced single-ion anisotropy. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure reveal multiple charge transfer pathways that lead to frustrated charge redistribution, diminishing the enhancement of ferromagnetic superexchange and yielding balanced competing interactions. First-principles calculations further validate that this canted antiferromagnetic state is an intermediate phase during the doping-driven antiferromagnetic-to-ferromagnetic transition. Our work not only clarifies the longstanding magnetic state controversy but also advances mechanistic understanding of charge transfer in this system, paving the way for the rational design of half-metallic van der Waals magnets toward practical spintronic devices.<\/jats:p>","DOI":"10.1021\/jacs.6c07616","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T14:33:48Z","timestamp":1785854028000},"page":"33295-33303","source":"Crossref","is-referenced-by-count":0,"title":["Emergent Canted Antiferromagnetism\nfrom Frustrated\nCharge Transfer in Half-Metal Candidate MnPSe3"],"prefix":"10.1021","volume":"148","author":[{"given":"Shilong","family":"Liu","sequence":"first","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanan","family":"Pan","sequence":"additional","affiliation":[{"name":"Hefei University of Technology , , ,","place":["Hefei, China, 230009"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-1618-4372","authenticated-orcid":true,"given":"Fei","family":"Ding","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huaze","family":"Sun","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shuxin","family":"Guo","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenbiao","family":"Jiao","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haining","family":"Liu","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lihao","family":"Qin","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Changping","family":"Wang","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ye","family":"Yang","sequence":"additional","affiliation":[{"name":"Hefei University of Technology , , ,","place":["Hefei, China, 230009"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-2693-9162","authenticated-orcid":true,"given":"Baolei","family":"Kang","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8891-260X","authenticated-orcid":true,"given":"Qiang","family":"Li","sequence":"additional","affiliation":[{"name":"Qingdao University , , ,","place":["Qingdao, China, 266071"]},{"name":"University of Waterloo , , ,","place":["Ontario, Canada, N2L 3G1"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,3]]},"reference":[{"issue":"7729","key":"2026081410110681800_cit1","doi-asserted-by":"publisher","first-page":"47","DOI":"10.1038\/s41586-018-0631-z","article-title":"Magnetism in two-dimensional van\nder Waals materials","volume":"563","author":"Burch","year":"2018","journal-title":"Nature"},{"issue":"5696","key":"2026081410110681800_cit2","doi-asserted-by":"publisher","first-page":"666","DOI":"10.1126\/science.1102896","article-title":"Electric Field Effect\nin Atomically Thin Carbon Films","volume":"306","author":"Novoselov","year":"2004","journal-title":"Science"},{"issue":"7729","key":"2026081410110681800_cit3","doi-asserted-by":"publisher","first-page":"94","DOI":"10.1038\/s41586-018-0626-9","article-title":"Gate-tunable\nroom-temperature ferromagnetism in two-dimensional Fe3GeTe2","volume":"563","author":"Deng","year":"2018","journal-title":"Nature"},{"issue":"24","key":"2026081410110681800_cit4","doi-asserted-by":"publisher","first-page":"10849","DOI":"10.1021\/jacs.0c04101","article-title":"Parasitic\nFerromagnetism in Few-Layered Transition-Metal Chalcogenophosphate","volume":"142","author":"Bai","year":"2020","journal-title":"J. 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Sci."},{"issue":"16","key":"2026081410110681800_cit24","doi-asserted-by":"publisher","first-page":"11169","DOI":"10.1103\/PhysRevB.54.11169","article-title":"Efficient\niterative schemes for ab initio total-energy\ncalculations using a plane-wave basis set","volume":"54","author":"Kresse","year":"1996","journal-title":"Phys.\nRev. B"},{"issue":"18","key":"2026081410110681800_cit25","doi-asserted-by":"publisher","first-page":"8207","DOI":"10.1063\/1.1564060","article-title":"Hybrid functionals\nbased on a screened\nCoulomb potential","volume":"118","author":"Heyd","year":"2003","journal-title":"J. Chem. Phys."},{"issue":"37","key":"2026081410110681800_cit26","doi-asserted-by":"publisher","first-page":"1802151","DOI":"10.1002\/adfm.201802151","article-title":"New Frontiers on van der Waals Layered Metal\nPhosphorous\nTrichalcogenides","volume":"28","author":"Wang","year":"2018","journal-title":"Adv. Funct. Mater."},{"issue":"44","key":"2026081410110681800_cit27","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.abj3106","article-title":"Magnon-phonon\nhybridization in 2D antiferromagnet MnPSe3","volume":"7","author":"Mai","year":"2021","journal-title":"Sci. Adv."},{"issue":"4","key":"2026081410110681800_cit28","doi-asserted-by":"publisher","first-page":"137105","DOI":"10.1007\/s11467-018-0796-9","article-title":"Tunable electronic\nstructure and magnetic coupling in strained two-dimensional semiconductor\nMnPSe3","volume":"13","author":"Pei","year":"2018","journal-title":"Front. Phys."},{"key":"2026081410110681800_cit29","doi-asserted-by":"publisher","first-page":"154432","DOI":"10.1016\/j.jallcom.2020.154432","article-title":"Exploring\nthe magnetic ordering in atomically thin antiferromagnetic MnPSe3 by Raman spectroscopy","volume":"828","author":"Liu","year":"2020","journal-title":"J. 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A"}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c07616","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/31\/33295\/66359068\/jacs.6c07616.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/31\/33295\/66359068\/jacs.6c07616.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T14:32:36Z","timestamp":1786717956000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/31\/33295\/5238579\/Emergent-Canted-Antiferromagnetism-from-Frustrated"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,3]]},"references-count":37,"journal-issue":{"issue":"31","published-online":{"date-parts":[[2026,8,3]]},"published-print":{"date-parts":[[2026,8,12]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c07616","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,3]]}}}