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Herein, we report a humidity\u2010responsive Cu(II) vapochromic complex based on reversible iodide coordination. A series of Cu(II) tetramine complexes with 1\n                    <jats:italic>R<\/jats:italic>\n                    ,2\n                    <jats:italic>R<\/jats:italic>\n                    \u2010cyclohexanediamine (chxn), including [Cu\n                    <jats:sup>II<\/jats:sup>\n                    (chxn)\n                    <jats:sub>2<\/jats:sub>\n                    (H\n                    <jats:sub>2<\/jats:sub>\n                    O)]Br\n                    <jats:sub>2<\/jats:sub>\n                    (\n                    <jats:bold>1<\/jats:bold>\n                    ) and [Cu\n                    <jats:sup>II<\/jats:sup>\n                    (chxn)\n                    <jats:sub>2<\/jats:sub>\n                    (H\n                    <jats:sub>2<\/jats:sub>\n                    O)\n                    <jats:sub>2<\/jats:sub>\n                    ]I\n                    <jats:sub>2<\/jats:sub>\n                    (\n                    <jats:bold>2<\/jats:bold>\n                    ), were synthesized and characterized by single\u2010crystal x\u2010ray diffraction. Complex\n                    <jats:bold>2<\/jats:bold>\n                    adopts a discrete hydrated structure, unlike the previously reported chain\u2010type [Cu\n                    <jats:sup>II<\/jats:sup>\n                    (chxn)\n                    <jats:sub>2<\/jats:sub>\n                    I]I. Whereas the chloride and bromide analogues exhibited little or no color change upon humidity variation, complex\n                    <jats:bold>2<\/jats:bold>\n                    displayed rapid and reversible vapochromism, changing from bluish purple to bluish green under low humidity or vacuum. Powder x\u2010ray diffraction and IR spectroscopy revealed reversible structural changes associated with water adsorption and desorption. UV\u2010Vis spectroscopy showed a pronounced red shift of the d\u2013d transition band upon dehydration. Electron spin resonance measurements combined with density functional theory calculations indicate that dehydration promotes axial coordination of iodide ions to Cu(II), yielding a [Cu\n                    <jats:sup>II<\/jats:sup>\n                    (chxn)\n                    <jats:sub>2<\/jats:sub>\n                    I\n                    <jats:sub>2<\/jats:sub>\n                    ] species in the solid state. These findings demonstrate a new vapochromic mechanism based on reversible iodide coordination at Cu(II) centers, providing a promising strategy for designing humidity\u2010responsive chromic materials.\n                  <\/jats:p>","DOI":"10.1002\/chem.71834","type":"journal-article","created":{"date-parts":[[2026,10,23]],"date-time":"2026-10-23T03:26:23Z","timestamp":1792725983000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Reversible Humidity\u2010Induced Vapochromism of a Cu(II) Tetramine Complex Driven by Iodide Access"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2999-8842","authenticated-orcid":false,"given":"Masanori","family":"Wakizaka","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry and Bioscience, Faculty of Science and Technology Chitose Institute of Science and Technology  Chitose Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3503-6161","authenticated-orcid":false,"given":"Hisaaki","family":"Tanaka","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry and Bioscience, Faculty of Science and Technology Chitose Institute of Science and Technology  Chitose Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-6999-6701","authenticated-orcid":false,"given":"Tetsu","family":"Sato","sequence":"additional","affiliation":[{"name":"Institute of Multidisciplinary Research for Advanced Materials Tohoku University  Sendai Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6739-8119","authenticated-orcid":false,"given":"Shinya","family":"Takaishi","sequence":"additional","affiliation":[{"name":"Department of Chemistry Graduate School of Science, Tohoku University Sendai Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5739-7326","authenticated-orcid":false,"given":"Masahiro","family":"Yamashita","sequence":"additional","affiliation":[{"name":"School of Chemical Science and Engineering Tongji University  Shanghai P.R. 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