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Meanwhile, the applications of functional CPPs have received increasing attention. In this paper, we first present a staged macrocyclization and TMS\u2010I exchange strategy for the precise synthesis of [12]CPP\u20108I, while a direct three\u2010fold macrocyclization of a diiodo\u2010terphenyl precursor yields [9]CPP\u20106I in 39% yield. These results not only provide reliable routes to iodinated CPPs, but also reveal the influence of ring size on their chemical reactivity. Second, we further synthesized the giant porphyrin\u2010CPP conjugates [12]CPP\u20108\n                    <jats:italic>t<\/jats:italic>\n                    Bu\n                    <jats:sub>3<\/jats:sub>\n                    TPP and [9]CPP\u20106\n                    <jats:italic>t<\/jats:italic>\n                    Bu\n                    <jats:sub>3<\/jats:sub>\n                    TPP from the respective iodinated precursors via Suzuki coupling with the porphyrin boronic ester. The unique 3D structure of the CPP scaffold can weaken intermolecular \u03c0\u2013\u03c0 stacking and favor the intermolecular loose packing of porphyrin units, ushering in generating\n                    <jats:sup>1<\/jats:sup>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    and O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>\u00b7\u2212<\/jats:sup>\n                    with high efficiency under light irradiation in DMF. Third, the giant porphyrin\u2010CPP conjugates, in particular [9]CPP\u20106\n                    <jats:italic>t<\/jats:italic>\n                    Bu\n                    <jats:sub>3<\/jats:sub>\n                    TPP, were demonstrated to be efficient photocatalysts for the photochemical reaction between tertiary aniline and maleimide with high yield and wide substrate scope, significantly outperforming porphyrins and other benchmark catalysts reported previously. Furthermore, the utility of [9]CPP\u20106\n                    <jats:italic>t<\/jats:italic>\n                    Bu\n                    <jats:sub>3<\/jats:sub>\n                    TPP as the photocatalyst for developing photoinduced polymerization was explored.\n                  <\/jats:p>","DOI":"10.1002\/anie.202522603","type":"journal-article","created":{"date-parts":[[2025,11,20]],"date-time":"2025-11-20T06:51:54Z","timestamp":1763621514000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Giant Cycloparaphenylene\u2010Scaffolded Porphyrins as Photocatalysts"],"prefix":"10.1002","volume":"65","author":[{"given":"Yu","family":"Ren","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Organic Solids Institute of Chemistry Chinese Academy of Sciences  Beijing 100190 China"},{"name":"School of Chemical Sciences University of Chinese Academy of Sciences  Beijing 101408 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yang\u2010Yang","family":"Zhang","sequence":"additional","affiliation":[{"name":"Fundamental Science Center of Rare Earths Ganjiang Innovation Academy Chinese Academy of Sciences  Ganzhou 341000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3433-7464","authenticated-orcid":false,"given":"Hong\u2010Guang","family":"Jin","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering Changsha University of Science &amp; 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