Self-Assembled Charge-Transfer Chiral ?-Materials: Stimuli-Responsive Circularly Polarized Luminescence and Chiroptical Photothermic Effects

Despite significant achievements in the field of chiroptical organic materials, the full utilization of both the excited state and ground state chiroptical properties in a single supramolecular system is still rarely disclosed. Here, we report that the rational combination of the charge-transfer (CT) interaction with the spacer effect and controlled protonation of pi-histidine leads to chiroptical organic pi-materials with both circularly polarized luminescence (CPL) and the supramolecular chirality-directed chiroptical photothermic effect. Three pyrene-conjugated histidine derivatives with varied acyl linkers (PyHis, PyC1His, and PyC3His) were designed to coassemble with electron-deficient 1,2,4,5-tetracyanobenzene (TCNB), leading to the formation of supramolecular CT complexes with intense orange to red CPL depending on the linker length. The linker length also affected the protonation-induced CPL responsiveness of the corresponding CT assemblies. Upon protonation of the histidine moiety, PyC3His/TCNB CT assemblies exhibited an inverted CPL signal, while PyHis/TCNB pairs gave quenched CPL due to the disassembly. The protonation-controlled PyC3His/TCNB CT assemblies at varied pH values showed different chiroptical photothermic effects (CPEs) for the same incident chiral light despite the molecular chirality of PyC3His remaining unchanged, supporting an interesting supramolecular chirality-directed photothermic effect.