Phosphorescent Chiral Cationic Binuclear Iridium(III) Complexes: Boosting the Circularly Polarized Luminescence Brightness

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2024-12-16 DOI:10.1021/acs.inorgchem.4c04271

Pierre-Henri Lanoë, Christian Philouze, Florian Molton, Nicolas Vanthuyne, Debsouri Kundu, Mathias Delporte--Pebay, Jeanne Crassous, Camille Latouche, Frédérique Loiseau

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Abstract

We report the synthesis and characterization of two chiral binuclear iridium(III) complexes (ΛΛ and ΔΔ) prepared from enantiopure building blocks [μ-Cl₂(Δ-Ir(C^N)₂)₂] and [μ-Cl₂(Λ-Ir(C^N)₂)₂]. These building blocks have been obtained by chiral preparative high-performance liquid chromatography of the neutral iridium(III) complex Irpiv (piv = 2,2,6,6-tetramethylheptane-3,5-dionate) followed by selective degradation of the ancillary ligand. For comparison purposes, we also synthesized a monomer (IrL¹) and a dimer (Ir₂L², mixture). All the complexes exhibit similar emission properties, emitting in the orange-red region of the spectra with a good photoluminescence quantum yield (λ_max = 610–625 nm, Φ ∼ 25%, τ ∼ 800–900 ns). However, the ΛΛ and ΔΔ complexes are optically active, indicating that no isomerization occurred during the different synthetic steps, as evidenced by both the circular dichroism spectra and their circularly polarized luminescence (CPL). The capital gain of the dimers (Ir₂L², ΛΛ, and ΔΔ) is a 4-fold brightness (B₃₈₀ = ε_380 nm × Φ) compared to the monomer (IrL¹) and the CPL brightness (B_CPL = B₃₈₀ × g_lum/2) of the binuclear complexes being among the highest reported to date for chiral iridium(III) complexes.

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我们报告了两种手性双核铱(III)配合物（ΛΛ和ΔΔ）的合成和表征，这两种配合物是由不纯结构单元[μ-Cl2(Δ-Ir(C^N)2)2]和[μ-Cl2(Λ-Ir(C^N)2)2]制备的。这些构件是通过中性铱（III）络合物 Irpiv（piv = 2,2,6,6-四甲基庚烷-3,5-二酸酯）的手性制备型高效液相色谱法，然后选择性地降解辅助配体而得到的。为了进行比较，我们还合成了单体（IrL1）和二聚体（Ir2L2，混合物）。所有复合物都表现出相似的发射特性，在光谱的橙红色区域发射，具有良好的光致发光量子产率（λmax = 610-625 nm，Φ ∼ 25%，τ ∼ 800-900 ns）。然而，从圆二色光谱和圆偏振发光（CPL）可以看出，ΛΛ和ΔΔ复合物具有光学活性，表明在不同的合成步骤中没有发生异构化。二聚体（Ir2L2、ΛΛ和ΔΔ）的资本增益是单体（IrL1）的 4 倍（B380 = ε380 nm × Φ），双核配合物的 CPL 亮度（BCPL = B380 × glum/2）是迄今为止报告的手性铱（III）配合物中最高的。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.