An attempt to develop a chiral luminescent probe with enantioselectivity is described. A tris(chelated) iridium(III) complex with bulky ligands, [Ir(bzq)₂(phen)]⁺ (bzqH = benzo[h]quinoline; phen = 1,10-phenanthroline), was synthesized and optically resolved into Δ- and Λ-enantiomers. The complex (denoted as Ir(III)) was emissive in non-polar organic solvents, while in aprotic and protic polar solvents it was less emissive. When Ir(III) was adsorbed by the colloidal particles of synthetic saponite (denoted as SAP), it recovered its emitting capability even in a solvent containing water. Emission from Ir(III) adsorbed by SAP was quenched by adding [Ru(acac)₃] (acac = acetylacetonato, denoted as Ru(III)). The Stern–Volmer constant (K_SV) exhibited remarkable stereoselectivity; K_SV = 15 900 ± 900 M⁻¹ for Δ-Ir(III)/Δ-[Ru(acac)₃] (or Λ-Ir(IIII)/Λ-[Ru(acac)₃]) and 7000 ± 500 M⁻¹ for Δ-Ir(III)/Λ-[Ru(acac)₃] (or Λ-Ir(III)/Δ-[Ru(acac)₃]). The dependence of the emission lifetime on the concentration of Ru(III) indicated that quenching proceeded dynamically. On the basis of the molecular model, it was postulated that a microscopic pocket surrounded by the bulky ligands at the top of adsorbed Ir(III) acted as a site discriminating the chirality of an approaching molecule.

中文翻译：

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三（螯合）铱（iii）配合物中的微观手性口袋，是动态对映选择性猝灭的位点†

描述了开发具有对映选择性的手性发光探针的尝试。合成了具有庞大配体[Ir（bzq）₂（phen）] ⁺（bzqH =苯并[ h ]喹啉； phen = 1,10-菲咯啉）的三（螯合）铱（III）配合物，并将其光学拆分为Δ -和Λ-对映体。该络合物（表示为Ir（III））在非极性有机溶剂中发射，而在非质子和质子极性溶剂中则发射较少。当Ir（III）被合成皂石（表示为SAP）的胶体颗粒吸附时，即使在含有水的溶剂中，它也恢复了其发射能力。来自Ir（发射III由SAP吸附）通过加入淬灭的[Ru（ACAC）₃ ]（acac =乙酰丙酮，表示为Ru（ III））。斯特恩-沃尔默常数（ K _SV）表现出显着的立体选择性。ķ _SV = 15 900±900米^-1为Δ-IR（ III）/Δ-的[Ru（ACAC） ₃ ]（或Λ-IR（I III）/Λ-的[Ru（ACAC） ₃ ]）和7000±对于Δ-Ir（ III）/Λ-[Ru（acac） ₃ ]（或Λ-Ir（ III）/Δ-[Ru（acac） ₃ ]）为500 M ^-1。发射寿命与Ru（ III）浓度的关系）表示淬火是动态进行的。根据分子模型，假定被吸附的Ir（III）顶部被庞大的配体包围的微观口袋充当了区分接近分子手性的位点。