We report herein the regioselective synthesis of all-carbon lemniscular nanohoops bis-po-CC and bis-pm-TC by the rational control of ring closures at the different positions of planar chiral tetrasubstituted [2.2]paracyclophane. Topological analyses reveal that bis-pm-TC is topologically chiral while bis-po-CC is topologically achiral. X-ray crystal analysis demonstrates that bis-pm-TC adopts a lemniscular conformation with a contiguous conjugation. CD and CPL measurements further reveal that the chiroptical properties of bis-pm-TC are obviously different from those of bis-po-CC due to their different topological chiralities.
In this study, we synthesized and reported the heterotopic bisnanohoops P5-[8,10]CPPs containing cycloparaphenylenes (CPPs) and a pillar[5]arene unit, which act not only as energy donors but also as a host for binding energy acceptors. We demonstrated that a series of elegant FRET systems could be constructed successfully through self-assembly between donors P5-[8,10]CPPs and acceptors with different emissions via host–guest interaction. These FRET systems further allow us to finely adjust the donors P5-[8,10]CPPs and acceptors (BODIPY-Br and Rh-Br) for achieving multiple color-tunable emissions, particularly white-light emission. More importantly, these host–guest complexes were successfully utilized in the fabrication of white-light fluorescent films and further integrated with a 365 nm LED lamp to create white LED devices. The findings highlight a new application of carbon nanorings in white-light emission materials, beyond the common recognition of π-conjugated molecules.
17 October 2022 in Journal of the American Chemical Society
Despite having significant applications in building nanomachines, molecular rotors with the rotational speed modulations to multiple stages in a wide range of frequency have not yet been well established. Here, we report the discovery of a stimuli-responsive molecular rotor, the rotational speed of which in the slow-to-fast range could be modulated to at least four stages triggered by acid/base and metal cations. The rotor itself rotates rapidly at ambient or elevated temperature but displays a restricted rotation after deprotonation due to the produced intramolecular electrostatic repulsion. Subsequent addition of Li+ or Na+ cations introduces an electrostatic bridge to stabilize the transition state of the deprotonated rotor, thus giving a cation-radius-dependent acceleration of the rotation to render the rotor running at a mid-speed. All the stimuli are highly reversible. Our studies provide a conceptual approach for constructing multistage rotational-speed-changing molecular rotors, and further, the practical nanomachines.