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Selective hydrogen atom transfer (HAT) in the \u03b1\u2010position of the 4N chain enables the free radical polymerization of various polar and nonpolar monomers. The tetrazene units play a dual role. Its decomposition generates aminyl radicals that can undergo HAT with another tetrazene molecule and lead to initiating C\u2010centered radicals. Contrary to what was previously thought the aminyl radicals never add to the monomers. The polymers obtained feature tetrazene chain ends, which can be harnessed as macro\u2010initiators to further grow the polymer chains. Heating of the former above the ceiling temperature leads to cleavage of the tetrazene function, which enables depolymerization by unzipping of polymethyl methacrylate (PMMA) and polystyrene (PS).<\/jats:p>","DOI":"10.1002\/anie.202425279","type":"journal-article","created":{"date-parts":[[2025,3,13]],"date-time":"2025-03-13T23:19:44Z","timestamp":1741907984000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Radical Chemistry of Tetrazenes: Access to Polymers with Pristine Tetrazenyl Chain Ends and Depolymerization Applications"],"prefix":"10.1002","volume":"64","author":[{"given":"Laetitia","family":"Bourgeois","sequence":"first","affiliation":[{"name":"Universite Claude Bernard Lyon 1  CNRS, CNES, ArianeGroup, LHCEP, B\u00e2t. 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