Double [5]carbohelicene: facile synthesis, chiroptical properties, isomerization study, and lasing application

Abstract

Double carbohelicenes have attracted considerable attention due to their aesthetic structures, distinct π-conjugation extension, inherent chirality, and intriguing optical and electronic properties. Herein, the concise de novo synthesis of a new double [5]carbohelicene 1 together with its chiroptical properties, isomerization process and lasing application is presented. 1 was synthesized by a simple protocol involving the formation of a 6,6′-bipentacene as the key intermediate. It is worth noting that 1 existed as two diastereomers 1-PP/MM and 1-PM, which were successfully isolated and unambiguously confirmed by X-ray crystallography. The optical resolution of the racemic 1-PP/MM was successfully achieved by chiral-phase high-performance liquid chromatography (HPLC), and 1-PP and 1-MM were characterized by circular dichroism. Interestingly, it was found that 1-PP/MM could be completely isomerized to 1-PM upon heating, and the detailed thermodynamics and kinetics of the isomerization process were systematically investigated. 1-PM exhibited deep-red luminescence with emission maximum at 723 nm and fluorescence quantum yield as high as 32.95%. Consequently, we can showcase the lasing application of 1-PM by doping with epoxy resin to assemble a bottle microlaser spontaneously, which the lasing wavelength is 796.6 nm at a threshold of 0.8 mJ cm⁻². We believe that our studies, including the facile synthesis methodology, detailed isomerization studies, and lasing application, will shed some light on the design and synthesis of novel carbohelical systems with more functions.