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A strained triple nanohoop with a shared central benzene unit is synthesized using a threefold intramolecular ring-closing approach. Among the five possible constitutional isomers, the isomer with the highest D 3h symmetry is isolated, the structure of which contains three nanohoop blades and a central hexaphenylbenzene unit. The structure is elucidated using NMR spectroscopy and mass spectrometry. The optical and electrochemical properties are investigated, revealing a moderate fluorescence quantum yield of 40 %. A water-soluble nanomaterial is prepared using a nanoparticle encapsulation method, and a fluorescence quantum yield of 10 % is retained, which demonstrates the potential of the nanomaterial in biological systems., (© 2024 Wiley-VCH GmbH.)

Delocalized organic π-radicals are intrinsically amphoteric redox systems; however, achieving their multistage redox capability presents a challenge. In addition, their instability often hampers their synthesis, isolation, and characterization. Herein, we report the synthesis of a stable π-extended nanographene π-radical (NR1) and its isolation in the crystalline form. NR1 exhibits an unusual four-stage amphoteric redox behavior, as revealed by cyclic voltammetry measurements. The stable charged species, including a cation and a radical dication, are characterized using spectroscopic methods. This study demonstrates that π-extension could serve as a viable approach to unlock the multistage redox ability of delocalized organic radicals., (© 2024 Wiley-VCH GmbH.)

The synthesis of bench-stable conjugated π-radicals is challenging owing to the lack of modular approaches, which greatly hampers their practical material screens and applications. Here, we demonstrate a spin-distribution-directed regioselective substitution strategy to introduce substituents into the specific positions of an olympicenyl radical in a stepwise manner, resulting in a series of highly stable radical species. The substituents can also adjust the crystal packing by means of steric and electronic factors, enabling the changing from a π-dimer to a pseudo-one-dimensional chain. The first single crystal organic field-effect transistor device based on a graphenic radical is fabricated in air, showing a hole mobility of up to 0.021 cm 2  V -1  s -1 and excellent device stability. This approach may be generalized to diverse spin-delocalized open-shell organic radicals., (© 2023 Wiley-VCH GmbH.)

Chiral shape-persistent molecular nanocarbons are promising chiroptical materials; their synthesis, however, remains a big challenge. Herein, we report the facile synthesis and chiral resolution of a double-stranded figure-eight carbon nanobelt 1 in which two [5]helicene units are fused together. Two synthetic routes were developed, and, in particular, a strategy involving Suzuki coupling-mediated macrocyclization followed by Bi(OTf) 3 -catalyzed cyclization of vinyl ether turned out to be the most efficient. The structure of 1 was confirmed by X-ray crystallographic analysis. The isolated (P,P)- and (M,M)- enantiomers show persistent chiroptical properties with relatively large dissymmetric factors (|g abs |=5.4×10 -3 and |g lum |=1.0×10 -2 ), which can be explained by the effective electron delocalization along the fully conjugated belt and the unique D 2 symmetry. 1 exhibits local aromatic character with a dominant structure containing eight Clar's aromatic sextet rings., (© 2023 Wiley-VCH GmbH.)

A stable nanohoop radical (OR3) combining the structures of cycloparaphenylene and an olympicenyl radical is synthesized and isolated in the crystalline state. X-ray crystallographic analysis reveals that OR3 forms a unique head-to-tail dimer that further aggregates into a one-dimensional chain in the solid state. Variable-temperature NMR and concentration-dependent absorption measurements indicate that the π-dimer is not formed in solution. An energy decomposition analysis indicates that van der Waals interactions are the driving force for the self-association process, in contrast with other olympicenyl derivatives that favor π-dimerization. The physical properties in solution phase have been studied, and the stable cationic species obtained by one-electron chemical oxidation. This study offers a new molecular design to modulate the self-association of organic radicals for overcoming the spin-Peierls transition, and to prepare novel nanohoop compounds with spin-related properties., (© 2023 Wiley-VCH GmbH.)