Stereo-control on Lanthanide Triple-stranded Helicates Toward Enhanced Enantioselective Sensing

Abstract

Chiral metal-organic cages (MOCs) serve as a representative model for enzyme simulation, offering a robust platform for reproducing and expanding enzyme functions at the molecular level. In this study, we present a family of lanthanide triple-stranded helicates with finely-tuned stereoconfigurations, self-assembled from ligands featuring both point and axial chiral centers. Circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy demonstrated that peripheral point chirality induces the stereoconfiguration (Δ/Λ) of the metal center, while bridging axial chirality defines the cavity chiral microenvironment, resulting in the formation of both homochiral and mesomeric helicates. In comparison to mesocate, the homochiral helicates exhibited heightened enantioselectivity in the luminescent detection of D/L-leucinol.

Keywords

Metal-organic cage / Stereocontrolled self-assembly / Lanthanide helicate / Chiral sensing

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