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However, insights into these mechanisms at the molecular orbital level remain elusive. Herein, we present large-scale density functional theory calculations to elucidate how synergistic effects arise from the combination of d atomic orbitals into molecular orbitals between M1 and M2 sites, with notable variations observed from M1\u2013N3\u2013M2\u2013N3\u2013C to M1\u2013N4\u2013M2\u2013N4\u2013C. We identify an average weakening of M1\/M2\u2013N bond strength in M1\u2013N3\u2013M2\u2013N3\u2013C relative to M1\u2013N4\u2013M2\u2013N4\u2013C, which is attributed to a shift from direct dx2\u2013y2 orbital overlap to nitrogen-mediated interactions involving the hybridization of bridge nitrogen 2p orbitals. Using hydrogen as a model adsorbate, we demonstrate that hydrogen adsorption on M1\u2013N3\u2013M2\u2013N3\u2013C shifts from wild modulation via a bridge configuration to mild modulation through an end-on configuration, signifying a selective orbital coupling from dx2\u2013y2 to dz2 orbitals. In contrast, hydrogen adsorption on M1\u2013N4\u2013M2\u2013N4\u2013C exhibits only mild modulation via an end-on configuration. This behavior is ascribed to the symmetry constraints of antibonding (d-d\/d*)-p* molecular orbitals near the Fermi level, mediated by nitrogen-mediated dz2-dz2* molecular orbitals. Furthermore, machine learning analyses corroborate these coordination environment-dependent synergistic mechanisms. Our findings provide a comprehensive molecular orbital-level understanding of how the interplay between coordination environments and electronic structures influences the properties of M1M2N6 catalysts, thereby establishing a theoretical framework for enhanced DACs design.<\/jats:p>","DOI":"10.1021\/jacs.6c08871","type":"journal-article","created":{"date-parts":[[2026,7,16]],"date-time":"2026-07-16T16:40:56Z","timestamp":1784220056000},"page":"31359-31368","source":"Crossref","is-referenced-by-count":1,"title":["Role\nof Coordination Environment in Synergistic Catalysis:\nA Molecular Orbital Perspective on M1M2N6 Catalysts"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2341-2422","authenticated-orcid":true,"given":"Zhangsheng","family":"Shi","sequence":"first","affiliation":[{"name":"City University of Hong Kong , , ,","place":["Hong Kong SAR, PR China, 999077"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ziyang","family":"Wu","sequence":"additional","affiliation":[{"name":"Donghua University , , ,","place":["Shanghai, China, 201620"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zheng","family":"Shu","sequence":"additional","affiliation":[{"name":"National University of Singapore , , ,","place":["Singapore, Republic of Singapore, 117543"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2686-466X","authenticated-orcid":true,"given":"Xin","family":"Wang","sequence":"additional","affiliation":[{"name":"City University of Hong Kong , , ,","place":["Hong Kong SAR, PR China, 999077"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,16]]},"reference":[{"key":"2026073109205383700_cit1","doi-asserted-by":"publisher","first-page":"634","DOI":"10.1038\/nchem.1095","article-title":"Single-atom catalysis\nof CO oxidation using Pt1\/FeOx","volume":"3","author":"Qiao","year":"2011","journal-title":"Nat. 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