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In this work, we report the first successful synthesis of a set of three nitrate supramolecular polymorphs (C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    N\n                    <jats:sub>4<\/jats:sub>\n                    )(NO\n                    <jats:sub>3<\/jats:sub>\n                    ) (\u03b1\u2010, \u03b2\u2010, and \u03b3\u2010phases) by a pH\u2010modulation secondary\u2010bond strategy, via the assembly of two types of \u03c0\u2010conjugated planar primitives. Solutions of different pH result in differing orientation of secondary bonds between [C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    N\n                    <jats:sub>4<\/jats:sub>\n                    ] and [NO\n                    <jats:sub>3<\/jats:sub>\n                    ] primitives. Secondary bonds dominate the packing of primitives in crystal lattices; varying these secondary bonds can afford NCS or centrosymmetric nitrate supramolecular polymorphs, with 2D \u03b1\u2010phase irreversibly transformed to 2D \u03b2\u2010phase in a solution of appropriate pH. These two polymorphs display distinctly different SHG responses and birefringences, ascribed to variation in stacking of 2D hydrogen\u2010bond layers resulting from the differing environmental pH. Supramolecular crystal structures comparison and theoretical studies confirm the crucial role played by secondary\u2010bond interactions between adjacent primitives in the rare nitrate supramolecular polymorphs. This work paves the way in elucidating the supramolecular polymorph transition\u2010mechanisms and correlating the polymorph structures and their NLO properties, and thereby discloses a new paradigm for development of high\u2010performance NCS materials with tailored optical properties.\n                  <\/jats:p>","DOI":"10.1002\/anie.202503136","type":"journal-article","created":{"date-parts":[[2025,3,12]],"date-time":"2025-03-12T03:53:31Z","timestamp":1741751611000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":28,"title":["pH\u2010Dependent Switching Between Nonlinear\u2010Optical\u2010Active Nitrate\u2010Based Supramolecular Polymorphs"],"prefix":"10.1002","volume":"64","author":[{"given":"Qiao","family":"Xia","sequence":"first","affiliation":[{"name":"China\u2010Australia Joint Research Center for Functional Molecular Materials School of Chemical Science and Engineering Tongji University  Shanghai 200092 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