Carbazole‐Dendronized Luminescent Radicals

Xiaotian, Rui; Ota, Wataru; Sato, Tohru; Furukori, Minori; Nakayama, Yasuo; Hosokai, Takuya; Hisamura, Eri; Nakamura, Kazuhiro; Matsuda, Kenshiro; Nakao, Kohei; Monkman, Andrew P.; Albrecht, Ken

doi:10.1002/anie.202302550

Cited by 15 publications

(14 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Strikingly, the maximum fluorescence emission wavelength of SD-2 red-shifts to 998 nm with a huge Stokes shift of 386 nm in tetrahydrofuran. Such a remarkably long emission maximum, to the best of our knowledge, represents the longest fluorescence emission wavelength for the organic fluorescent radicals reported to date (see Figure S41 and Figure for comparison with representative radical emitters). − …”

Section: Resultsmentioning

confidence: 71%

Sulfone-Functionalized Chichibabin’s Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm

Zhou,

Yang,

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

While monoradical emitters have emerged as a new route toward efficient organic light-emitting diodes, the luminescence property of organic diradicaloids is still scarcely explored. Herein, by devising a novel radical−radical coupling-based synthetic approach, we report a new class of sulfone-functionalized Chichibabin's hydrocarbon derivatives, SD-1−3, featuring varied substituent patterns and moderate to high diradical characters of 0.44−0.70, as highly stable diradicaloids with rarely seen NIR emission beyond 900 nm. Via comprehensive experimental and theoretical investigations, we reveal that the optoelectronic and magnetic properties of these materials are significantly tuned by the variations of substitutions (H/CF 3 /OMe) on the molecular skeletons. More importantly, quantum chemical computations indicate that the embedding of sulfone groups has contributed to a breaking of their quasi-C 2 symmetry of these diradicaloid molecules and results in an excited-state charge transfer character. Therefore, a remarkably deep NIR emissive wavelength of up to 998 nm, together with a large Stokes shift (∼386 nm), is achieved for the CF 3 -based SD-2 molecule in tetrahydrofuran. To the best of our knowledge, such a luminescent wavelength of SD-2 has represented the longest wavelengths among the currently reported organic fluorescent radicals. Overall, our work not only establishes a new synthetic approach toward stable Chichibabin's hydrocarbons but also paves the way for designing NIR emissive open-shell materials with both fundamental understanding and feasible control of their luminescent properties.

show abstract

Section: Resultsmentioning

confidence: 71%

Sulfone-Functionalized Chichibabin’s Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm

Zhou,

Yang,

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…It is important to note here that the fluorescence wavelength of triarylmethyl radical derivatives has been controlled in many cases by extending the conjugation length. 30–32 This should probably be interpreted in terms of the cyano group of DAAN radicals, which allows the two aromatic rings to adopt a near-planar conformation and thus amplifies the resonance effect of the substituents. These results represent an important aspect of the design and control of the fluorescence wavelength of fluorescent radicals.…”

Section: Resultsmentioning

confidence: 99%

Diverse metastable diarylacetonitrile radicals generated by polymer mechanochemistry

Yamamoto,

Aoki,

Mikami

et al. 2024

RSC Mechanochem.

View full text Add to dashboard Cite

show abstract

“…Moving to larger molecules, second, third and fourth-generation carbazole dendronized TTM radicals have been explored by Albrecht et al 162 (Fig. 28).…”

Section: Radical Emittersmentioning

confidence: 99%