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Trimetallic complexes of the type (MN2S2)2Cu (M = [FeNO]2+ or [VO]2+), in which these two redox-active S = 1\/2 spin probes are linked by a diamagnetic Cu(I) center in a tetrahedral S4 coordination environment, are developed. Structural analysis shows that the Cu(I) bridge enforces a twisted arrangement of the two MN2S2 units, in contrast to square-planar NiS4-bridged analogues, [ Quiroz, M.; et al., Chem. Sci.2023, 14, 9167\u20139174]. leading to distinct metal\u2013ligand orbital alignment and sulfur-mediated bonding pathways. Despite a large interspin separation of approximately 6 \u00c5 between the spin probes, magnetic susceptibility measurements reveal appreciable ferromagnetic exchange coupling between these paramagnetic centers, although weaker than the coupling observed for the d8 (M\u2032 = Ni(II), Pd(II), and Pt(II))-bridged stair-step complexes. These differences are attributed to the contrasting geometries of the CuS4 and M\u2032S4 cores and their impact on superexchange through the bridging sulfurs. In addition to the solid-state X-ray crystallography, this new class of trimetallics was characterized by multiple methods including electrochemistry, vibrational spectroscopy, magnetic susceptibility, EPR, Mo\u0308ssbauer, and DFT computations. Redox and vibrational studies further probe electronic communication between the FeNO units: \u03bd(NO) stretching frequency indicates that one-electron reduction is largely localized on a single FeNO center, whereas two-electron reduction leads to electron delocalization across both units. Together, these results demonstrate that copper-imposed geometric distortion modulates sulfur-mediated spin coupling and electron delocalization, providing design principles for multimetallic, spin-active architectures.<\/jats:p>","DOI":"10.1021\/acsorginorgau.6c00057","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T14:04:27Z","timestamp":1785852267000},"page":"636-653","source":"Crossref","is-referenced-by-count":0,"title":["Twists, Turns,\nand Spins: Copper-Guided Electronic\nCommunication in Sulfur-Bridged Trimetallic Complexes"],"prefix":"10.1021","volume":"6","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4326-9152","authenticated-orcid":true,"given":"Akhil K.","family":"Singh","sequence":"first","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dakota D.","family":"Jones","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aruzhan","family":"Abdikaiym","sequence":"additional","affiliation":[{"name":"University of Alabama , , , ,","place":["Tuscaloosa, Alabama, United States, 35487"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2671-3581","authenticated-orcid":true,"given":"Naushad","family":"Ahmed","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sarnali","family":"Sanfui","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Joseph H.","family":"Reibenspies","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4132-3565","authenticated-orcid":true,"given":"Yisong","family":"Guo","sequence":"additional","affiliation":[{"name":"Carnegie Mellon University , , , ,","place":["Pittsburgh, Pennsylvania, United States, 15213"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7432-6332","authenticated-orcid":true,"given":"Brad S.","family":"Pierce","sequence":"additional","affiliation":[{"name":"University of Alabama , , , ,","place":["Tuscaloosa, Alabama, United States, 35487"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kim R.","family":"Dunbar","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3263-3219","authenticated-orcid":true,"given":"Michael B.","family":"Hall","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0070-2075","authenticated-orcid":true,"given":"Marcetta Y.","family":"Darensbourg","sequence":"additional","affiliation":[{"name":"Texas A&M University , , , ,","place":["College Station, Texas, United States, 77843"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,31]]},"reference":[{"key":"2026100709064218900_cit1","doi-asserted-by":"publisher","first-page":"653","DOI":"10.1126\/science.277.5326.653","article-title":"Iron-Sulfur Clusters: Nature\u2019s\nModular, Multipurpose Structures","volume":"277","author":"Beinert","year":"1997","journal-title":"Science"},{"issue":"2","key":"2026100709064218900_cit2","doi-asserted-by":"publisher","first-page":"825","DOI":"10.1021\/cr020619e","article-title":"Synthetic\nAnalogues of Cysteinate-Ligated Non-Heme Iron and Non-Corrinoid Cobalt\nEnzymes","volume":"104","author":"Kovacs","year":"2004","journal-title":"Chem. 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Chem."},{"key":"2026100709064218900_cit21","doi-asserted-by":"publisher","first-page":"393","DOI":"10.1021\/acsorginorgau.3c00025","article-title":"Sulfur\nLone Pairs Control Topology in Heterotrimetallic\nComplexes: An Experimental and Theoretical Study","volume":"3","author":"Guerrero-Almaraz","year":"2023","journal-title":"ACS Org. Inorg. Au"},{"issue":"21","key":"2026100709064218900_cit22","doi-asserted-by":"publisher","first-page":"15975","DOI":"10.1021\/acs.inorgchem.1c00987","article-title":"Linear\nand Bent Nitric Oxide Ligand Binding in an Asymmetric Butterfly Complex:\nCoMoCo\u2032","volume":"60","author":"Guerrero-Almaraz","year":"2021","journal-title":"Inorg. Chem."},{"issue":"11","key":"2026100709064218900_cit23","doi-asserted-by":"publisher","first-page":"5248","DOI":"10.1021\/cr500659u","article-title":"Metallodithiolates\nas Ligands in Coordination, Bioinorganic,\nand Organometallic Chemistry","volume":"115","author":"Denny","year":"2015","journal-title":"Chem. 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Biol."},{"key":"2026100709064218900_cit30","doi-asserted-by":"publisher","first-page":"567","DOI":"10.1126\/science.1075843","article-title":"A Ni-Fe-Cu\nCenter in a Bifunctional Carbon Monoxide Dehydrogenase\/ Acetyl-Coa\nSynthase","volume":"298","author":"Doukov","year":"2002","journal-title":"Science"},{"key":"2026100709064218900_cit31","doi-asserted-by":"publisher","first-page":"10328","DOI":"10.1021\/jacs.7b03892","article-title":"Multielectron Chemistry\nwithin a Model Nickel Metalloprotein: Mechanistic Implications for\nAcetyl-CoA Synthase","volume":"139","author":"Manesis","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026100709064218900_cit32","doi-asserted-by":"publisher","first-page":"12116","DOI":"10.1021\/jacs.2c02580","article-title":"Toward Improved\nCharge Separation through Conformational Control in Copper Coordination\nComplexes","volume":"144","author":"Griffin","year":"2022","journal-title":"J. Am. Chem. 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Chem."},{"key":"2026100709064218900_cit35","doi-asserted-by":"publisher","first-page":"1411","DOI":"10.1126\/science.aap9437","article-title":"The biosynthesis\nof methanobactin","volume":"359","author":"Kenney","year":"2018","journal-title":"Science"},{"issue":"5","key":"2026100709064218900_cit36","doi-asserted-by":"publisher","first-page":"5436","DOI":"10.1021\/jacs.5c19068","article-title":"Mixed-Valent Tetracopper\nDisulfides\nSupported by a 1,8-Naphthyridine-Based Ligand: Models for Electronic\nCommunication in Biological Copper Systems","volume":"148","author":"See","year":"2026","journal-title":"J. Am. Chem. 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