Cun Yang, J Z Liu, Haoxuan Zhang, Yijun Lin, Jinquan Chen, Hiroyuki Furuta, Chuanhu Lei
Circularly polarized luminescence (CPL) based on π-conjugated macrocycles holds great promise in diverse fields. However, developing chiral macrocycles that combine long-wavelength emission (e.g., near-infrared, NIR) and high CPL brightness ( B CPL ) remains a significant challenge. In this study, we present a new approach to achieve intense NIR CPL by engineering an expanded porphyrinoid system featuring an excitonically coupled BODIPY array. This architecture is built upon a 9,9′-spirobifluorene-embedded dodecaphyrin that supports an extended π-conjugation macrocycle with a rigid, lemniscular topology. Such a design confers persistent chirality and exceptional CPL performance at the far-red/NIR-I boundary. Specifically, a broad emission spanning 600–835 nm centered at 704 nm was observed, with a maximum g lum of 0.007 and a B CPL as high as 255.1 M –1 cm –1 at 693 nm. This work thus not only demonstrates how rational structural design enables efficient NIR-active CPL, but also highlights the potential of expanded porphyrinoids as a versatile blueprint for next-generation chiral optoelectronic materials.