“Matching Rule” for Generation, Modulation and Amplification of Circularly Polarized Luminescence

Abstract

Circularly polarized luminescence (CPL) generated by chiral luminescent systems has sparked enormous attention in multidisciplinary field as it brings infinite potential for applications, such as 3D optical displays, biological probes, and chiroptical sensors. Satisfying both the conditions of chirality and luminescence (including fluorescence or phosphorescence) is a prerequisite for constructing CPL materials. In this regard, whether in organic, inorganic, or hybrid systems, chiral and luminescent components generally involve effective coupling through covalent or noncovalent bonds. For covalent interactions, such as the copolymerization of chiral and luminescent monomers, although covalent bonds provide high stability for the system, they inevitably involve tedious preparation procedures that connect chirality and luminescence together. For noncovalent bonds, take supramolecular assembly as an example, chiral elements and achiral light-emitting units are chiral transferred through intermolecular interactions, and their advantages include the diversity of luminescent and chiral building blocks, the stimuli responsiveness brought by noncovalent bonds, as well as the potential amplification of CPL signals by coassembly. However, the stability of the assembly system may be poor, and the assembly chiroptical performance and morphology are difficult to predict. Gratifyingly, matching rule that do not rely on covalent together with noncovalent interactions allows for the effortless construction, modulation, as well as amplification of CPL systems.

In this Account, we overview different strategies based on matching rule, including fluorescence-selective absorption, circularly polarized reflection, and circularly polarized fluorescence energy transfer (CPF-ET). Examples of these strategies are illustrated with a focus on helical polymers in light of their appealing structures and wide uses. For instance, for fluorescence-selective absorption, chiral helical polymers can convert racemic fluorescence light into a circularly polarized one with specific handedness by simply overlapping the helical polymer’s circular dichroism (CD) spectra with the luminophore’s emission spectra. For circularly polarized reflection, employing the selective reflection of certain handedness’s circularly polarized light, the high helical twisting power (HTP) of the helical polymer in the cholesteric liquid crystals (N*-LCs) gives the system high g_lum. Additionally, for CPF-ET, only the emission spectrum of the donor and the absorption (or excitation) spectrum of the achiral acceptor are required to overlap, and no covalent or noncovalent interactions between the two are required. An outlook for the CPL materials related to matching rule which will avail the optimization and extension of this intriguing approach concludes the Account. We hope that the Account will offer insightful inspiration for the flourishing progress of chiroptical systems and present exciting opportunities.