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Here we report a series of terarylene derivatives (1o\u20133o) that undergo photoinduced cyclization to generate ion pairs with distinct reactivity profiles. Spectroscopic studies combined with density functional theory calculations reveal that ion-pair formation strongly depends on the leaving group and solvent polarity. While 1o readily generates a highly stable cationic species upon irradiation even in nonpolar media, 2o and 3o exhibit alternative pathways involving neutral closed intermediates or other photoinduced processes. These differences give rise to markedly different photochemical behaviors in polar and nonpolar media. Notably, the photoinduced ion pairs exhibit catalytic activity in ring-opening polymerization reactions. Whereas 1o promotes self-initiated cationic polymerization, 2o and 3o require external protic initiators under the conditions examined, while the specific catalytic role of the counteranion was assumed as a working hypothesis. These findings provide structure\u2013reactivity insights for controlling photoinduced ion-pair formation and demonstrate their potential as light-activated catalysts.<\/jats:p>","DOI":"10.1021\/acsami.6c15826","type":"journal-article","created":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T09:03:33Z","timestamp":1789722213000},"page":"52837-52847","source":"Crossref","is-referenced-by-count":0,"title":["Photoinduced Ion Pair Generator Based on Triangle Terarylene"],"prefix":"10.1021","volume":"18","author":[{"given":"Taichi","family":"Muto","sequence":"first","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]},{"name":"NAIST\u2013Universit\u00e9 de Toulouse , , 118 Route de Narbonne , ,","place":["Toulouse Cedex 9, France, 31062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kaho","family":"Irie","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chigusa","family":"Goto","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kei","family":"Maruyama","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fumina","family":"Tsutsui","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yoshiko","family":"Nishikawa","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5186-3867","authenticated-orcid":true,"given":"Tsuyoshi","family":"Ando","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1956-8777","authenticated-orcid":true,"given":"Tsumoru","family":"Morimoto","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3789-6600","authenticated-orcid":true,"given":"Mihoko","family":"Yamada","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]},{"name":"Institute of Science and Engineering, Kanazawa University , , Kakuma-machi , ,","place":["Kanazawa, Japan, 920-1192"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9566-3573","authenticated-orcid":true,"given":"Tsuyoshi","family":"Kawai","sequence":"additional","affiliation":[{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]},{"name":"NAIST\u2013Universit\u00e9 de Toulouse , , 118 Route de Narbonne , ,","place":["Toulouse Cedex 9, France, 31062"]},{"name":"Nara Institute of Science and Technology (NAIST) , , 8916-5 Takayama , , ,","place":["Ikoma, Nara, Japan, 630-0192"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,18]]},"reference":[{"key":"2026093002084331300_cit1","doi-asserted-by":"publisher","first-page":"474","DOI":"10.1038\/nchembio.98","article-title":"Allosteric Regulation and Catalysis Emerge via a Common Route","volume":"4","author":"Goodey","year":"2008","journal-title":"Nat. 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