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Stepwise Amplification of Circularly Polarized Luminescence in Chiral Metal Cluster Ensembles
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Stepwise Amplification of Circularly Polarized Luminescence in Chiral Metal Cluster Ensembles
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Journal Article
Stepwise Amplification of Circularly Polarized Luminescence in Chiral Metal Cluster Ensembles
2023
Overview
Chiral metal‐organic frameworks (MOFs) are usually endowed by chiral linkers and/or guests. The strategy using chiral secondary building units in MOFs for solving the trade‐off of circularly polarized luminescence (CPL)‐active materials, high photoluminescence quantum yields (PLQYs) and high dissymmetry factors (|glum|) has not been demonstrated. This work directionally assembles predesigned chiral silver clusters with ACQ linkers through reticular chemistry. The nanoscale chirality of the cluster transmits through MOF's framework, where the linkers are arranged in a quasi‐parallel manner and are efficiently isolated and rigidified. Consequently, this backbone of chiral cluster‐based MOFs demonstrates superb CPL, high PLQYs of 50.3%, and |glum| of 1.2 × 10−2. Crystallographic analyses and DFT calculations show the quasi‐parallel arrangement manners of emitting linkers leading to a large angle between the electric and magnetic transition dipole moments, boosting CPL response. As compared, an ion‐pair‐direct assembly without interactions between linkers induces one‐ninth |glum| and one‐sixth PLQY values, further highlighting the merits of directional arrangement in reticular nets. In addition, a prototype CPL switching fabricated by a chiral framework is controlled through alternating ultraviolet and visible light. This work is expected to inspire the development of reticular chemistry for high‐performance chiroptical materials. Chiral transfer and circularly polarized luminescence activity are successfully achieved by assembling ACQ molecules with chiral Ag clusters in chiral silver cluster‐based assembled materials. The chiral reticular self‐assembly exhibits markedly enhanced luminescence efficiency and glum values compared to those of the ion‐pair‐direct assembly through a well‐defined spatial arrangement and highly efficient synergy.
Publisher
John Wiley & Sons, Inc,John Wiley and Sons Inc,Wiley
