Work

Dispersion Forces‐Driven Hierarchical Assembly of Protein‐Like Lanthanide Octamers and Emergent CPL

Year: 2024

Type: article

Abstract: Hierarchical self‐assembly driven by non‐covalent interactions is a prevalent strategy employed by nature to construct sophisticated biomacromolecules, such as proteins. However, the construction of protein‐like superstructures that rely on weaker dispersion forces‐driven hierarchical assembly remains largely unexplored. Here, we report the first example of dispersion forces driving the high‐order assembly of the lanthanide trinuclear circular helicate [HNEt₃]₃[Eu₃(LL)₆] (ΔΔΔ‐1) into a protein‐like lanthanide octamer ((ΔΔΔ‐1)₈‐2). Within the octamer, the forty‐eight (48) menthol groups on the ligands and eighty‐four (84) 1,4‐dioxane solvent molecules contribute to enhanced dispersion forces through conformational adaptation and size‐matching effects. These enhanced dispersion forces not only drive the formation of the hierarchical superstructure but also result in a four‐level chirality transfer from the menthol to the octamer. Benefiting from the homochirality of Eu3+, the octamer is endowed the strong circularly polarized emission (|glum|=0.34, Φoverall=41 %). This understanding of how dispersion forces drive hierarchical self‐assembly provides a foundation for the directed fabrication of more fascinating superstructures.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202403976