Reversal of chirality in solutions and aggregates of chiral tetrachlorinated diperylene diimides towards efficient circularly polarized light detection

Abstract

Helicenes exhibit promise as active layer materials for circularly polarized light (CPL) detectors due to their strong chiroptical activity. However, their practical application is limited by the complicated synthesis and loosely solid-state packing. This study introduces a chiral induction strategy towards the synthesis of helicene derivatives, chiral tetrachlorinated diperylene diimides ((SSSS)-4CldiPDI or (RRRR)-4CldiPDI). When incorporating the chiral (S/R)-1-cyclohexylethyl (Cy) substituents, the chirality is directly transferred to the π-aromatic core and forms the PP- or MM-helicene subunit. Notably, (SSSS)-Cy induces preferred PP helicity while (RRRR)-Cy leads to the MM helicity in the monomers. However, these molecules exhibit reversed chirality in crystals, where (SSSS)-Cy controls MM helicity and (RRRR)-Cy induces PP helicity. Theoretical calculations reveal that the (SSSS)-PP structure demonstrates lower energy distribution in monomers, whereas the (SSSS)-MM structure exhibits lower energy in crystals. Then, the CPL detection based on n-type PDI-helicene derivatives is achieved by using (SSSS)-4CldiPDI or (RRRR)-4CldiPDI crystals. The maximum photocurrent dissymmetry factor g_ph of +0.16 for (RRRR)-4CldiPDI and −0.15 for (SSSS)-4CldiPDI is obtained. Our work demonstrates a novel chiral induction strategy for designing helicene-based materials with both high dissymmetry factor and large charge carrier mobility, which offers great potential for the advancement of CPL detection.