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This family of star\u2010shaped polyarenes can be regarded as three acenes that are connected through a single benzene ring. In fact, just like acenes, unsubstituted large starphenes are poorly soluble and highly reactive molecules under ambient conditions making their synthesis difficult to achieve. Herein, we report two different synthetic strategies to obtain a starphene formed by 19\n                    <jats:italic>cata<\/jats:italic>\n                    \u2010fused benzene rings distributed within three hexacene branches. This molecule, which is the largest starphene that has been obtained to date, was prepared by combining solution\u2010phase and on\u2010surface synthesis. [19]Starphene was characterized by high\u2010resolution scanning tunneling microscopy (STM) and spectroscopy (STS) showing a remarkable small HOMO\u2010LUMO transport gap (0.9\u2005eV).\n                  <\/jats:p>","DOI":"10.1002\/anie.202411861","type":"journal-article","created":{"date-parts":[[2024,8,7]],"date-time":"2024-08-07T12:37:15Z","timestamp":1723034235000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["[19]Starphene: Combined In\u2010Solution and On\u2010Surface Synthesis Towards the Largest Starphene"],"prefix":"10.1002","volume":"63","author":[{"given":"Javier","family":"Besteiro\u2010S\u00e1ez","sequence":"first","affiliation":[{"name":"Centro de Investigaci\u00f3n en Qu\u00edmica Biol\u00f3xica e Materiais Moleculares (CiQUS) and Departamento de Qu\u00edmica Org\u00e1nica Universidade de Santiago de Compostela  15782 Santiago de Compostela Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luis M.","family":"Mateo","sequence":"additional","affiliation":[{"name":"Centro de Investigaci\u00f3n en Qu\u00edmica Biol\u00f3xica e Materiais Moleculares (CiQUS) and Departamento de Qu\u00edmica Org\u00e1nica Universidade de Santiago de Compostela  15782 Santiago de Compostela Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sergio","family":"Salaverr\u00eda","sequence":"additional","affiliation":[{"name":"Nanomaterials and Nanotechnology Research Center (CINN) CSIC-UNIOVI-PA  33940 El Entrego Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6545-5028","authenticated-orcid":false,"given":"Tao","family":"Wang","sequence":"additional","affiliation":[{"name":"Donostia International Physics Center  20018 San Sebasti\u00e1n 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Oviedo Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amador","family":"Garc\u00eda\u2010Fuente","sequence":"additional","affiliation":[{"name":"Physics Department University of Oviedo  33007 Oviedo Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jaime","family":"Ferrer","sequence":"additional","affiliation":[{"name":"Physics Department University of Oviedo  33007 Oviedo Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0877-5938","authenticated-orcid":false,"given":"Dolores","family":"P\u00e9rez","sequence":"additional","affiliation":[{"name":"Centro de Investigaci\u00f3n en Qu\u00edmica Biol\u00f3xica e Materiais Moleculares (CiQUS) and Departamento de Qu\u00edmica Org\u00e1nica Universidade de Santiago de Compostela  15782 Santiago de Compostela Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8592-1284","authenticated-orcid":false,"given":"Martina","family":"Corso","sequence":"additional","affiliation":[{"name":"Donostia International Physics Center  20018 San Sebasti\u00e1n Spain"},{"name":"Centro de F\u00edsica de Materiales (CFM-MPC) CSIC-UPV\/EHU  Donostia 20018 San Sebasti\u00e1n Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dimas G.","family":"de Oteyza","sequence":"additional","affiliation":[{"name":"Nanomaterials and Nanotechnology Research Center (CINN) CSIC-UNIOVI-PA  33940 El Entrego Spain"},{"name":"Donostia International Physics Center  20018 San Sebasti\u00e1n Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3814-589X","authenticated-orcid":false,"given":"Diego","family":"Pe\u00f1a","sequence":"additional","affiliation":[{"name":"Centro de Investigaci\u00f3n en Qu\u00edmica 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