64797 2025 eng 1 8 46 147 article American Chemical Society (ACS) 1 -- -- -- In this proof-of-concept study, we show that polyfluorinated trityl radicals with the, to this date, highest fluorination grade can be accessed in quantitative yields in a straightforward manner starting from the perfluorinated trityl cation. The trityl skeleton is functionalized with trimethylsilyl halides to yield perhalofluoro trityl cations, which are subsequently reduced using commercial zinc powder. In this way, we prepare three perhalofluoro trityl radicals and analyze the impact of the fluorine ligands on their electro-optical properties, revealing some interesting trends. In comparison to literature-known polychlorinated trityl radicals, the new polyfluorinated derivatives exhibit substantially higher fluorescence quantum yields, longer luminescence lifetimes, and an expanded emission range that extends into the yellow spectral region. They further display enhanced photostability under light irradiation. In radical-stained polystyrene nanoparticles, an additional broad emission band in the red−NIR wavelength region is observed, which is attributed to excimer formation. Finally, the stability of the new radicals is investigated under ambient conditions, showing the slow conversion with atmospheric oxygen yielding the respective peroxides, which are characterized by single-crystal X-ray diffraction. All in all, our study extends the present scope of luminescent trityl radicals, as the functionalization of the perfluorinated cationic precursor unlocks the path toward a vast variety of polyfluorinated trityl radicals. Journal of the American Chemical Society 0002-7863 10.1021/jacs.5c16418 urn:nbn:de:kobv:b43-647973 true journal-article https://creativecommons.org/licenses/by/4.0/ crossref PersonAuthorFirstName_1,PersonAuthorLastName_1,PersonAuthorIdentifierOrcid_1,PersonAuthorFirstName_2,PersonAuthorLastName_2,PersonAuthorIdentifierOrcid_2,PersonAuthorFirstName_3,PersonAuthorLastName_3,PersonAuthorFirstName_4,PersonAuthorLastName_4,PersonAuthorFirstName_5,PersonAuthorLastName_5,PersonAuthorFirstName_6,PersonAuthorLastName_6,PersonAuthorIdentifierOrcid_6,PersonAuthorFirstName_7,PersonAuthorLastName_7,PersonAuthorIdentifierOrcid_7,PersonAuthorFirstName_8,PersonAuthorLastName_8,PersonAuthorIdentifierOrcid_8,PersonAuthorFirstName_9,PersonAuthorLastName_9,PersonAuthorFirstName_10,PersonAuthorLastName_10,PersonAuthorIdentifierOrcid_10,PublisherName,TitleMain_1,Language,TitleParent_1,ArticleNumber,PublishedYear,IdentifierIssn,Enrichmentlocal_crossrefLicence doi-import 24.11.2025 false true Creative Commons - CC BY - Namensnennung 4.0 International Johanna Schlögl Alexander R. Krappe Paul C. Fürstenwerth Amelie L. Brosius Carlo Fasting Kurt F. Hoffmann Ute Resch-Genger Siegfried Eigler Simon Steinhauer Sebastian Riedel eng uncontrolled Dye eng uncontrolled Fluorescence eng uncontrolled Radical eng uncontrolled Synthesis eng uncontrolled Mechanism eng uncontrolled Signal enhancement eng uncontrolled Nano eng uncontrolled Particle eng uncontrolled Characterization eng uncontrolled Quantum yield eng uncontrolled Photophysics eng uncontrolled Lifetime eng uncontrolled Polarity eng uncontrolled Polymer eng uncontrolled Solvatchromism eng uncontrolled Excimer Analytische Chemie Ingenieurwissenschaften und zugeordnete Tätigkeiten 1 Analytische Chemie; Referenzmaterialien 1.2 Biophotonik Material Chemie und Prozesstechnik Chemische Charakterisierung und Spurenanalytik Verlagsliteratur Datei für die Öffentlichkeit verfügbar ("Open Access") Wissenschaftliche Artikel der BAM Advanced Materials Bundesanstalt für Materialforschung und -prüfung (BAM) https://opus4.kobv.de/opus4-bam/files/64797/JACS 2025_Luminescent Perhalofluoro Trityl Radicals.pdf