Enantioselective Phosphorescent Recognition via Engineered Chiral Microenvironments in Homochiral Ir(III) Metallohelices-Based Porous Crystals

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Abstract
Enantioselective recognition is pivotal in chemical biology and pharmaceutical science, yet achieving high-fidelity discrimination remains challenging. Drawing inspiration from natural helical architectures that create stereospecific microenvironments, we report a class of homochiral dinuclear Ir(III) metallohelices as modular building units for porous crystalline frameworks. The Λ2S6-DP and Δ2R6-DP metallohelices, assembled from enantiopure 1,2-diphenylethylenediamine (DPEN, RR- or SS-form) spacers and spatial-matching aldehyde-terminated fac-Ir(ppy)3 (Δ- or Λ-handed) vertices, organize into well-defined chiral channels through stereoregular C-H···π and aromatic stacking. These confined microenvironments cooperate with the intrinsic phosphorescence of Ir(III) centers to enable highly enantioselective sensing. The Λ2S6-DP framework exhibits distinct recognition for R-BINOL and D-Trp, with enantiomeric factors (EF) reaching 6.09 and 5.54, respectively, while its enantiomeric Δ2R6-DP counterpart shows the reversed preference. Crucially, replacing the spacer with a methoxy-substituted analogue disrupts the π-stacking network and erases enantiodiscrimination, confirming the essential role of aromatic-driven assembly in creating functional chiral spaces. This work establishes a modular strategy for constructing phosphorescent chiral microenvironments by organization of homochiral photoactive metallohelices that effectively discriminate enantiomers through differential phosphorescence response.
Funding Information
  • Natural Science Foundation of Liaoning Province (2024-MSLH-070)
  • Fundamental Research Funds for the Central Universities (DUT25Z2504)
  • National Natural Science Foundation of China (22171033, 22477014)

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