Air‐Stable Organoradical Boron Reagents

Li, Zenghui; Wang, Jing; Liu, Xiaoyang; Gao, Pin; Li, Guoping; He, Gang; Rao, Bin

doi:10.1002/anie.202302835

Cited by 11 publications

(1 citation statement)

References 68 publications

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“…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.

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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.

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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.

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Catalytic Undirected Meta‐Selective C–H Borylation of Metallocenes

Zheng,

Liu,

Wang

et al. 2023

Advanced Science

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Metallocenes are privileged backbones in the fields of synthetic chemistry, catalysis, polymer science, etc. Direct C–H functionalization is undoubtedly the simplest approach for tuning the properties of metallocenes. However, owing to the presence of multiple identical C(sp2)‐H sites, this protocol often suffers from low reactivity and selectivity issues, especially for the regioselective synthesis of 1,3‐difunctionalized metallocenes. Herein, an efficient iridium‐catalyzed meta‐selective C–H borylation of metallocenes is reported. With no need of preinstalled directing groups, this approach enables a rapid synthesis of various boronic esters based on benzoferrocenes, ferrocenes, ruthenocene, and related half sandwich complex. A broad range of electron‐deficient and ‐rich functional groups are all compatible with the process. Notably, C–H borylation of benzoferrocenes takes place exclusively at the benzene ring, which is likely ascribed to the shielding effect of pentamethylcyclopentadiene. The synthetic utility is further demonstrated by easy scalability to gram quantities, the conversion of boron to heteroatoms including N3, SePh, and OAc, as well as diverse cross‐coupling reactions.

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Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

Chang,

Arnold,

Blinder

et al. 2024

Angewandte Chemie

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Conjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise as building blocks in materials for quantum sensing and quantum information processing. However, it is a considerable challenge to design simple analogues of the Chichibabin hydrocarbon that are chemically inert, exhibit high diradical character and emit light at a distinct wavelength that may offer an optical readout of the spin state in functional ensembles. Here we describe the serendipitous discovery of the stable TTM‐TTM diradicaloid, which exhibits high diradical character, a striking sky‐blue color and near‐infrared (NIR) emission (in solution). This combination of properties is unique among related diradicaloids and is due to the presence of hydrogen and chlorine atoms in “just the right positions”, allowing a perfectly planar, yet predominantly benzenoid bridge to connect the two sterically stabilized radical centers. In‐depth studies of the optical and magnetic properties suggest that this structural motif could become a mainstay building block of organic spin materials.

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Air‐Stable Organoradical Boron Reagents

Cited by 11 publications

References 68 publications

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

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

Catalytic Undirected Meta‐Selective C–H Borylation of Metallocenes

Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

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