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A cascade of SCSC transformations driven by changes to anion<jats:bold>\u00b7\u00b7\u00b7<\/jats:bold>\u03c0 stabilisation sees two metastable species convert to a ground\u2010state form. This constitutes one of the most dramatic chemical effects yet attributed to anion<jats:bold>\u00b7\u00b7\u00b7<\/jats:bold>\u03c0 interactions. Metastable networks [Ag(\u00b5\u2010NO<jats:sub>2<\/jats:sub>)(pyz)] (<jats:bold>1<\/jats:bold>, <jats:bold>2<\/jats:bold>) are composed of dimerised (<jats:bold>1<\/jats:bold>) and delaminated (<jats:bold>2<\/jats:bold>) AgNO<jats:sub>2<\/jats:sub>\/pyrazine, which convert to the ground\u2010state [Ag(\u03ba<jats:sup>2<\/jats:sup>\u2010NO<jats:sub>2<\/jats:sub>)(pyz)] form <jats:bold>3<\/jats:bold> with 3D connectivity. The metastable phases show responsiveness to solvent vapour and temperature. This work shows how anion<jats:bold>\u00b7\u00b7\u00b7<\/jats:bold>\u03c0 interactions influence solid\u2010state structure with support from computational modelling and highlights how metastable materials may harness anion<jats:bold>\u00b7\u00b7\u00b7<\/jats:bold>\u03c0 interactions to deliver large structural and property changes.<\/jats:p>","DOI":"10.1002\/ejic.201700505","type":"journal-article","created":{"date-parts":[[2017,5,11]],"date-time":"2017-05-11T15:39:55Z","timestamp":1494517195000},"page":"2628-2636","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Anion\u00b7\u00b7\u00b7\u03c0 Interactions and Metastability: Structural Transformations in a Silver\u2013Pyrazine Network"],"prefix":"10.1002","volume":"2017","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6520-6216","authenticated-orcid":false,"given":"William J.","family":"Gee","sequence":"first","affiliation":[{"name":"Department of Chemistry 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