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Here, graphdiyne\u2010based sp\u2010carbon atoms are incorporated into the first coordination sphere of the metal complex, yielding an asymmetric sp\u2010C\n                    <jats:sub>2<\/jats:sub>\n                    \u2013M\u2013O\n                    <jats:sub>2<\/jats:sub>\n                    (M = Cu, Co, Ni) coordination geometry. During synthesis, hydrogen\u2010substituted graphdiyne (HsGDY) acts as a microporous polymeric ligand populated with periodically aligned diacetylene coordination sites, which spatially confine and arrange metal complexes within micropores featuring a dominant size of 1.5\u00a0nm. For the electrochemical NO reduction, the microporous framework of HsGDY, which is rich in sp\u2010carbons, accelerates NO mass transport, enabling elevated NO surface coverage even under diluted NO feeding streams. The electron\u2010donating sp\u2010carbons synergize with oxygen to tune the electronic structure of Cu\n                    <jats:sup>\u03b4+<\/jats:sup>\n                    (1 &lt;\n                    <jats:italic>\u03b4<\/jats:italic>\n                    &lt; 2), reducing the formation barrier of *HNO and thus achieving a high NH\n                    <jats:sub>3<\/jats:sub>\n                    Faradaic efficiency of 91.8% and a yield rate of 0.44\u00a0mg h\n                    <jats:sup>\u22121<\/jats:sup>\n                    cm\n                    <jats:sup>2<\/jats:sup>\n                    at 0.1\u00a0V versus a reversible hydrogen electrode (RHE). This work identifies graphdiyne\u2010based sp\u2010carbon atoms as viable constituents of the first coordination sphere of metal complexes, breaking the reliance on nitrogen, oxygen, and sulfur heteroatoms for constructing nonaxial asymmetric coordination geometries.\n                  <\/jats:p>","DOI":"10.1002\/anie.9566713","type":"journal-article","created":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T03:35:13Z","timestamp":1789529713000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Incorporation of Graphdiyne\u2010Based sp\u2010Carbon Into the First Coordination Sphere of a Metal Complex for the Electrocatalysis of Nitric Oxide to Ammonia"],"prefix":"10.1002","author":[{"given":"Jiahao","family":"Ma","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Xi'an Key Laboratory of Functional Organic Porous Materials Northwestern Polytechnical University  Xi'an 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