Lemniscular BODIPY Array of Expanded Porphyrinoids: A π-Conjugated Macrocycle Exhibiting Bright Near-Infrared...

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.