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However, the utility of this transformation is severely restrained by strong orbital interactions between metal sites and the lone pairs of N atoms that lead to irreversible catalyst deactivation. Here, we propose a Mn\n                    <jats:sub>3<\/jats:sub>\n                    Co\n                    <jats:sub>7<\/jats:sub>\n                    alloy electrocatalyst that triggers a high\u2010spin\u2010to\u2010low\u2010spin transition in Co. The flipped spin state originates from tuned\n                    <jats:italic>d<\/jats:italic>\n                    \u2010electron pairing, promoting electron occupation in antibonding orbitals and weakening the Co\u2013N bond. The reduced adsorption energy that facilitates the desorption of\n                    <jats:italic>N<\/jats:italic>\n                    \u2010heterocycles is revealed to be the key factor driving the improved catalytic durability. This strategy enables a scaled\u2010up electrosynthesis with a yield of 92.5% at 1.25 A to obtain 10\u00a0g of deuterated piperazine hydrochloride. The methodological universality of diverse unsaturated\n                    <jats:italic>N<\/jats:italic>\n                    \u2010heterocycles highlights the application potential.\n                  <\/jats:p>","DOI":"10.1002\/anie.7797032","type":"journal-article","created":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T16:22:26Z","timestamp":1785428546000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Flipped Spin\u2010State Resists Cobalt Poisoning for the Durable Electrocatalytic Deuteration of\n                    <i>N<\/i>\n                    \u2010Heterocyclic Compounds"],"prefix":"10.1002","volume":"65","author":[{"given":"Meng","family":"He","sequence":"first","affiliation":[{"name":"Department of Chemistry School of Science Tianjin University  Tianjin 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