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Herein, we present a copper(I) iodide\u2013sodium luminescent complex assembled with a hybrid phosphane\u2010phosphinate ligand. The photoemission of the tetrametallic {Cu\n                    <jats:sub>2<\/jats:sub>\n                    I\n                    <jats:sub>2<\/jats:sub>\n                    Na\n                    <jats:sub>2<\/jats:sub>\n                    } aggregate is consistent with the thermally activated delayed fluorescence that originates from the [CuI(phosphane)] motifs but strongly depends on the coordination environment of sodium ions completed by O\u2010donor solvent molecules, Na\u2013\u03c0(phenyl) interactions, and\/or Na\u2013I bonds. The reversible removal and vapor\u2010phase addition of methanol, ethanol, water, and dimethoxyethane as Na\u2010bound ligands alter the solid\u2010state luminescence from blue (461\u00a0nm) to yellow (570\u00a0nm) with quantum yields reaching 0.73. Importantly, different photoemission responses to methanol (522\u00a0nm) and ethanol (492\u00a0nm) are complemented by preferred binding of methanol and its detection in up to 1:10 methanol:ethanol mixtures. Variations of luminescence among the studied solvates are attributed to the alterations of secondary sphere interactions involving sodium ions and illustrate a new approach to stimuli\u2010responsive metal complexes constructed from soft\u2010hard donor ligands.\n                  <\/jats:p>","DOI":"10.1002\/anie.6117838","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T13:19:40Z","timestamp":1789478380000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Luminescence Vapochromism of a Cu(I)\/Na Phosphane Iodide Assembly Based on a Secondary\u2010Sphere Sodium Response"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-2825-1404","authenticated-orcid":false,"given":"Henna","family":"Korhonen","sequence":"first","affiliation":[{"name":"Department of Chemistry and Sustainable Technology University of Eastern Finland  Joensuu 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