Three cationic iridium complexes containing 4,7-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-1,10-phenanthroline (L(1)) and 4,7-bis(3',6'-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,9'-bi(9H-carbazol)-9-yl)-1,10-phenanthroline (L(2)) as the ancillary ligands, namely, [Ir(ppy)(2)(L(1))]PF(6) (1), [Ir(ppy)(2)(L(2))]PF(6) (2) and [Ir(oxd)(2)(L(2))]PF(6) (3) (ppy is 2-phenylpyridine, oxd is 2,5-diphenyl-1,3,4-oxadiazole), have been designed and prepared. With more intramolecular rotational units on the ancillary ligand (L(2)), 2 and 3 possess a unique aggregation-induced phosphorescent emission (AIPE) property. This phenomenon was unprecedentedly observed in the cationic iridium(III) complexes. In order to investigate the underlying mechanism of this AIPE behavior, their photophysical, temperature-dependent aggregation properties as well as theoretical calculations, were performed. The results suggest that restricted intramolecular rotation is responsible for the AIPE of cationic complexes. Moreover, photoluminescent quantum yields in the neat film, thermal stabilities and off/on luminescence switching of 2 were investigated, revealing its potential application as a candidate for LECs and organic vapor sensing.
A dendrimer PYTPAG2 composed of a central pyrene “core” and four exterior “arms” capped with electroactive triphenylamine is developed as an electroactive precursor to prepare fluorescent films through electropolymerization (EP). The fluorescence emission comes from the central pyrene “core” and the steric hindrance of the exterior “arms” is beneficial for the formation of microporous morphology. The stable and highly cross‐linked fluorescent EP films can be obtained even as free‐standing films. Further, these dendrimer EP films are first studied as the multifunctional fluorescent probe: the emission of EP films exposed to trinitrotoluene vapor is quenched by 82% in 120 s; while the fluorescence is increased to nearly 400% in 120 s upon exposure to benzene vapor, EP films also act as the fluorescent sensor to Fe3+ in solution and the limit of detection is obtained to be 8.5 × 10−8 m. All the above detection processes exhibit remarkable reversibility. These excellent performances are attributed to both the specific molecular features of PYTPAG2 and the intrinsic properties of EP films.
We report the synthesis and characterization of two cationic iridium(III) complexes with dendritic carbazole ligands as ancillary ligands, namely, [Ir(ppy)(2)L3]PF(6) (1) and [Ir(ppy)(2)L4]PF(6) (2), where L3 and L4 represent 3,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-1,10-phenanthroline and 3,8-bis(3',6'-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,9'-bi(9H-carbazol)-9-yl)-1,10-phenanthroline, respectively. Their photophysical properties have been investigated and compared. The results have shown that complex 2 is aggregation-induced phosphorescent emission (AIPE) active and exhibits the highest photoluminescent quantum yield (PLQY) of 16.2% in neat film among the reported cationic Ir(III) complexes with AIPE activity. In addition, it also enjoys redox reversibility, good film-forming ability, excellent thermal stability as well as off/on luminescence switching properties, revealing its potential application as a candidate for light-emitting electrochemical cells and organic vapor sensing. To explore applications in biology, 2 was used to image cells.
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