Construction of stable luminescent donor–acceptor neutral radicals: a theoretical study

Wang, Xin; Xue, Ping; Zhou, Cefeng; Zhang, Yewen; Li, Ping; Chen, Runfeng

doi:10.1039/d2tc03712b

Cited by 6 publications

(4 citation statements)

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“…49 For this purpose, a sphere was set up with the carbon-centred radical at the origin and a 6 Å radius; these dimensions are the most suitable to consider the spatial steric protection of the radical by the surrounding atoms. 50 The buried volumes and steric maps presented in this work were obtained using the SambVca 2 Web application. 51 According to the topography (Fig.…”

Section: Resultsmentioning

confidence: 99%

Diverse metastable diarylacetonitrile radicals generated by polymer mechanochemistry

Yamamoto,

Aoki,

Mikami

et al. 2024

RSC Mechanochem.

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Section: Resultsmentioning

confidence: 99%

Diverse metastable diarylacetonitrile radicals generated by polymer mechanochemistry

Yamamoto,

Aoki,

Mikami

et al. 2024

RSC Mechanochem.

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“…This section introduces luminescent polychlorinated TArM radicals, the most-studied group of luminescent radicals to date (Chart and Table ). The following discussion focuses on the TArM radicals that have been synthesized and isolated, although several computational studies have predicted various intriguing polychlorinated TArM radicals. − The discussion covers the basic luminescence properties of the polychlorinated TArM radicals, the current understanding of these radicals based on theoretical aspects, and major scientific advancements related to their unique luminescence properties. Figure summarizes representative or first well-established examples highlighting the development of luminescent polychlorinated TArM radicals.…”

Section: Luminescent Organic Radicalsmentioning

confidence: 99%

Luminescent Radicals

Mizuno,

Matsuoka,

Mibu

et al. 2024

Chem. Rev.

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Organic radicals are attracting increasing interest as a new class of molecular emitters. They demonstrate electronic excitation and relaxation dynamics based on their doublet or higher multiplet spin states, which are different from those based on singlet–triplet manifolds of conventional closed-shell molecules. Recent studies have disclosed luminescence properties and excited state dynamics unique to radicals, such as highly efficient electron–photon conversion in OLEDs, NIR emission, magnetoluminescence, an absence of heavy atom effect, and spin-dependent and spin-selective dynamics. These are difficult or sometimes impossible to achieve with closed-shell luminophores. This review focuses on luminescent organic radicals as an emerging photofunctional molecular system, and introduces the material developments, fundamental properties including luminescence, and photofunctions. Materials covered in this review range from monoradicals, radical oligomers, and radical polymers to metal complexes with radical ligands demonstrating radical-involved emission. In addition to stable radicals, transiently formed radicals generated in situ by external stimuli are introduced. This review shows that luminescent organic radicals have great potential to expand the chemical and spin spaces of luminescent molecular materials and thus broaden their applicability to photofunctional systems.

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“…49 For this purpose, a sphere was set up with the carbon-centered radical at the origin and a 6 Å radius; these dimensions are the most suitable to consider the spatial steric protection of the radical by the surrounding atoms. 50 The buried volumes and steric maps presented in this work were obtained using the SambVca 2 Web application. 51 According to the topography (Figure S124), the methoxy groups at the meta-position of the DAAN radicals protect the carbon-centered radicals well (Figure 7b).…”

Section: Synthesis Of the Daan Derivativesmentioning

confidence: 99%

Diverse Metastable Diarylacetonitrile Radicals Generated by Polymer Mechanochemistry

Yamamoto,

Aoki,

Mikami

et al. 2023

Preprint

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Fluorescent radicals have attracted great attention as luminescent materials, mostly on account of their potential to achieve higher luminescence efficiency than closed-shell molecules. However, analyzing fluorescent radicals at ambient conditions remains a challenging task, because radicals are usually unstable in air. In addition, to the best of our knowledge, research aimed at controlling fluorescence wavelengths through substituent changes has not yet been accomplished. Here, we report diverse metastable diarylacetonitrile (DAAN) radicals, which contain different substituents, generated by polymeric mechanochemical reactions. The DAAN radicals, generated by ball-milling powdered polystyrene together with DAAN derivatives, were dispersed within the polystyrene matrix, where they retained their radical state, which allowed measuring solid-state fluorescence spectra. These measurements revealed that a wide range of fluorescence wavelengths from green to red (λem,max = 517–635 nm) can be achieved only by changing the substituents on the aromatic rings in these DAAN radicals. This phenomenon has not been observed for the well-studied triarylmethyl radicals. The fluorescence wavelength of these DAAN radicals can be precisely estimated by time-dependent density-functional theory (TD-DFT) calculations. The amount of DAAN radicals generated upon ball-milling is discussed in conjunction with DFT calculations and experimental results. Our results suggest that the orbital interactions with polymeric mechanoradicals, the bond-dissociation enthalpy, and the steric protection of the radical center are of paramount importance for the generation of DAAN radicals. The results of this study can be expected to provide useful guidelines for the development of advanced fluorescent radicals.

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Construction of stable luminescent donor–acceptor neutral radicals: a theoretical study

Abstract: Stable luminescent donor–acceptor (D–A•) radical molecules with theoretically 100% internal quantum efficiency in emission have recently attracted a lot of attention, especially in light-emitting diodes. However, radicals are intrinsically highly...

Cited by 6 publications

References 50 publications

Diverse metastable diarylacetonitrile radicals generated by polymer mechanochemistry

Diverse metastable diarylacetonitrile radicals generated by polymer mechanochemistry

Luminescent Radicals

Diverse Metastable Diarylacetonitrile Radicals Generated by Polymer Mechanochemistry

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