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Here, we report a structural transformation in single crystals of 5,15\u2010bisphenyl\u2010tetrabenzoporphyrin (\n                    <jats:bold>Ph\u2010BP<\/jats:bold>\n                    ) triggered by the removal of intercalated\n                    <jats:italic>o<\/jats:italic>\n                    \u2010dichlorobenzene. This transformation induces a 90\u00b0 rotation of the \u03c0\u2010stacking direction between adjacent layers, giving rise to a previously unobserved long\u2010period polymorph characterized by the periodic alternation of two distinct herringbone packing motifs. The solvent\u2010desorption\u2010induced transformed phase can also be formed on Si\/SiO\n                    <jats:sub>2<\/jats:sub>\n                    substrates and affords single\u2010crystal organic field\u2010effect transistors exhibiting hole mobilities higher than those of devices based on the previously reported\n                    <jats:bold>Ph\u2010BP<\/jats:bold>\n                    polymorph. These findings suggest that solvent\u2010desorption\u2010induced structural transformations provide a viable strategy for accessing hidden polymorphs with enhanced semiconductor performance.\n                  <\/jats:p>","DOI":"10.1002\/advs.77915","type":"journal-article","created":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T18:00:31Z","timestamp":1790532031000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Solvent\u2010Desorption\u2010Induced Formation of a Long\u2010Period Polymorph Yielding a High\u2010Performance Porphyrin\u2010Based Organic Semiconductor"],"prefix":"10.1002","author":[{"given":"Kazuya","family":"Miyazaki","sequence":"first","affiliation":[{"name":"Institute for Chemical Research Kyoto University  Uji Kyoto 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