Structurally Diverse Pyrene‐decorated Planar Chiral [2,2]Paracyclophanes with Tunable Circularly Polarized Luminescence between Monomer and Excimer.

We reported the synthesis of a series of structurally diverse CPL‐active molecules, in which pyrene units were installed to chiral pm/po‐[2,2]PCP scaffolds either with or without a triple bond spacer for pm/po‐PCP‐P1 and pm/po‐PCP‐P2, respectively. The X‐ray crystallographic analyses revealed that these pyrene‐based [2,2]PCP derivatives exhibited diverse structures and crystal packings in the solid phases. The pyrene‐based [2,2]PCP derivatives exhibit various (chir)optical properties in organic solutions, depending on their respective structures. In a mixture of dioxane and water, pm/po‐PCP‐P1 emit green excimer fluorescence, whereas pm/po‐PCP‐P2 emit blue one. The chiroptical investigation demonstrated that Rp‐pm‐PCP‐P1 and Rp‐pm‐PCP‐P2 exhibited completely opposite CD and CPL signals even they possess the same chiral Rp‐[2,2]PCP core. The same argument also holds for other chiral pyrene‐based [2,2]PCP derivatives. The theoretical calculation revealed that these unusual phenomena were attributed to different orientation between transition electric dipole moments and the magnetic dipole moments originating from the presence or absence of a triple bond spacer. These pyrene‐based [2,2]PCP derivatives display various colours and fluorescence emissions in the solid state and PMMA films, possibly due to the different packings as observed in the crystal structure. Moreover, these compounds also can interact with perylene diimide through π‐π interactions, leading to near‐white fluorescence. [ABSTRACT FROM AUTHOR]