Guest‐Modulated Circularly Polarized Luminescence by Ligand‐to‐Ligand Chirality Transfer in Heteroleptic PdII Coordination Cages. Issue 35 (4th July 2022)

• Record Type: Journal Article
• Authors: Wu, Kai; Tessarolo, Jacopo; Baksi, Ananya; Clever, Guido H.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 35(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-07-04
• Subjects: Chirality Transfer -- Circularly Polarized Luminescence -- Coordination Cages -- Host–Guest Chemistry -- Supramolecular Chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202205725
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Multicomponent metallo‐supramolecular assembly allows the rational combination of different building blocks. Discrete multifunctional hosts with an accessible cavity can be prepared in a non‐statistical fashion. We employ our shape‐complementary assembly (SCA) method to achieve for the first time integrative self‐sorting of heteroleptic Pd II cages showing guest‐tunable circularly polarized luminescence (CPL). An enantiopure helicene‐based ligand (M or P configuration) is coupled with a non‐chiral emissive fluorenone‐based ligand (A or B ) to form a series of Pd2 L2 L′2 assemblies. The modular strategy allows to impart the chiral information of the helicenes to the overall supramolecular system, resulting in CPL from the non‐chiral component. Guest binding results in a 4‐fold increase of CPL intensity. The principle offers potential to generate libraries of multifunctional materials with applications in molecular recognition, enantioselective photo‐redox catalysis and information processing. Abstract : Integrative self‐assembly of Pd II cations with an enantiopure helicene‐based ligand and non‐chiral but emissive fluorenone ligands yields a series of Pd2 L2 L′2 heteroleptic coordination cages, showing circularly polarized luminescence (CPL) from the non‐chiral moiety. Modulation of the chiroptical properties is achieved by ligand modification or guest binding, achieving an up to 4‐fold enhancement of CPL intensity.