Thermally Activated Delayed Fluorescent (TADF) luminophores offer the potential to achieve 100% Internal Quantum Efficiency (IQE) by harvesting both singlet and triplet excitons via reverse intersystem crossing from T1 to S1. This class of molecules has therefore been embraced in the pursuit of cheaper and more efficient electrochemiluminescent (ECL) labels. The present study explores how tuning the electron-donating (D) and -accepting (A) strengths of peripheral substituents affects the ECL emission of mono- and dicyanoarene-based TADF dyes. To this end, we synthesized two series of TADF compounds, independently manipulating electron donors and acceptors by (i) halogenating electron-rich diphenylamine moieties, or (ii) mono- or di-substituting the electron-poor cyanoarene core with either fluorine or imidazole. Through a comparative analysis, we elucidate the role of each substituent in shaping the photophysics of the investigated luminophores. Despite only achieving a relative ΦECL as high as 1.27%, this framework identifies several molecular features that boost the ECL efficiency to pave the way for designing highly efficient TADF-based ECL emitters. Ultimately, imidazole substituents are exploited as a platform for functionalization with triethylene glycol units. The resulting water-soluble TADF luminophores are characterized under conditions usual to commercial ECL bioanalysis, proving their potential as a cost-effective alternative replacement to [Ru(bpy)3]2+ in clinical diagnostic.
Fracassa, A., Calogero, F., Pavan, G., Nikolaou, P., Fermi, A., Ceroni, P., et al. (2024). Tunable electrochemiluminescence of TADF luminophores: manipulating efficiency and unveiling water-soluble emitters. CHEMICAL SCIENCE, 15, 17892-17899 [10.1039/d4sc04986a].
Tunable electrochemiluminescence of TADF luminophores: manipulating efficiency and unveiling water-soluble emitters
Fracassa, Alessandro;Calogero, Francesco;Nikolaou, Pavlos;Fermi, Andrea;Ceroni, Paola;Paolucci, Francesco;Cozzi, Pier Giorgio;Negri, Fabrizia;Gualandi, Andrea
;Valenti, Giovanni
2024
Abstract
Thermally Activated Delayed Fluorescent (TADF) luminophores offer the potential to achieve 100% Internal Quantum Efficiency (IQE) by harvesting both singlet and triplet excitons via reverse intersystem crossing from T1 to S1. This class of molecules has therefore been embraced in the pursuit of cheaper and more efficient electrochemiluminescent (ECL) labels. The present study explores how tuning the electron-donating (D) and -accepting (A) strengths of peripheral substituents affects the ECL emission of mono- and dicyanoarene-based TADF dyes. To this end, we synthesized two series of TADF compounds, independently manipulating electron donors and acceptors by (i) halogenating electron-rich diphenylamine moieties, or (ii) mono- or di-substituting the electron-poor cyanoarene core with either fluorine or imidazole. Through a comparative analysis, we elucidate the role of each substituent in shaping the photophysics of the investigated luminophores. Despite only achieving a relative ΦECL as high as 1.27%, this framework identifies several molecular features that boost the ECL efficiency to pave the way for designing highly efficient TADF-based ECL emitters. Ultimately, imidazole substituents are exploited as a platform for functionalization with triethylene glycol units. The resulting water-soluble TADF luminophores are characterized under conditions usual to commercial ECL bioanalysis, proving their potential as a cost-effective alternative replacement to [Ru(bpy)3]2+ in clinical diagnostic.File | Dimensione | Formato | |
---|---|---|---|
d4sc04986a.pdf
accesso aperto
Tipo:
Versione (PDF) editoriale
Licenza:
Licenza per Accesso Aperto. Creative Commons Attribuzione (CCBY)
Dimensione
1.34 MB
Formato
Adobe PDF
|
1.34 MB | Adobe PDF | Visualizza/Apri |
d4sc04986a1.pdf
accesso aperto
Tipo:
File Supplementare
Licenza:
Licenza per Accesso Aperto. Creative Commons Attribuzione (CCBY)
Dimensione
7.34 MB
Formato
Adobe PDF
|
7.34 MB | Adobe PDF | Visualizza/Apri |
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.