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Enantioselective Phosphorescent Recognition via Engineered Chiral Microenvironments in Homochiral Ir(III)
Zhuolin Shi1,2, Xing Zhao2, Hanshu Li2
1Central Hospital of Dalian University of Technology, Dalian University of Technology, Dalian 116024, China.
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.
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