双环金属化Pd（II）配合物[Pd(C∧N∧C)(L)], L = PPh3, AsPh3， SbPh3的合成和光物理性质

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-03-27 DOI:10.1021/acs.inorgchem.4c05436

Rose Jordan, Sam Kler, Iván Maisuls, Niklas Klosterhalfen, Benjamin Dietzek-Ivanšić, Cristian A. Strassert, Axel Klein

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引用次数: 0

摘要

虽然含有双环金属化配体的铂（II）配合物作为三齿发光基团已经得到了很好的研究，但它们的Pd（II）对应物的合成可及性长期缺乏。受C∧N∧C配位模式（dpp2 - = 2,6-二（苯基-2-基）吡啶）合成[Pd(dpp)(PPh3)]的研究启发，我们根据自己对密切相关的Pt（II）基化合物的研究，通过优化合成工艺并探索其反应性，制备了一系列配合物[Pd(dpp)(PnPh3)] （Pn = P, As, Sb）。我们研究了Pd（C∧N∧C）配合物的电化学（循环伏安法）和光物理（紫外-可见吸收和发射，瞬态吸收（TA）光谱）性质，首次报道了它们的表征。我们观察到紫外-可见吸收带低至450 nm，电化学HOMO-LUMO间隙在3.2 V左右，不同的PnPh3配体变化最小。在时间分辨发射光谱和热释热光谱中观察到更明显的配体影响。[Pd(dpp)(AsPh3)]的光致发光量子产率最高（ΦL），达到0.06。光谱数据的解释由（TD-）DFT计算支持。此外，我们还报道了几种双核Pd（II）配合物的结构和光谱数据，包括前体{[Pd(dppH)(μ-Cl)]}2和敏感化合物[Pd(dpp)(PnPh3)]的多种分解产物。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Synthesis and Photophysics of the Doubly Cyclometalated Pd(II) Complexes [Pd(C∧N∧C)(L)], L = PPh3, AsPh3, and SbPh3

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Synthesis and Photophysics of the Doubly Cyclometalated Pd(II) Complexes [Pd(C∧N∧C)(L)], L = PPh3, AsPh3, and SbPh3

While Pt(II) complexes containing doubly cyclometalated ligands as tridentate luminophores are well studied, the synthetic accessibility of their Pd(II) counterparts was lacking for a long time. Inspired by a recent report on the synthesis of [Pd(dpp)(PPh₃)] involving the C^∧N^∧C coordination mode (with dpp^2– = 2,6-di(phenid-2-yl)pyridine) and following our own work on closely related Pt(II)-based compounds, we produced the series of complexes [Pd(dpp)(PnPh₃)] (Pn = P, As, Sb) by optimizing the synthetic procedure and exploring their reactivity in the process. Our study of the electrochemical (cyclic voltammetry) and photophysical (UV–vis absorption and emission, transient absorption (TA) spectroscopy) properties of the Pd(C^∧N^∧C) complexes represents the first report on their characterization. We observed UV–vis absorption bands down to 450 nm and electrochemical HOMO–LUMO gaps around 3.2 V, which show minimal variation with different PnPh₃ coligands. A more pronounced influence of the coligand was observed in time-resolved emission and TA spectroscopy. The highest photoluminescence quantum yield (Φ_L) in the series was found for [Pd(dpp)(AsPh₃)], reaching 0.06. The interpretation of the spectroscopic data is supported by (TD-)DFT calculations. Additionally, we report structural and spectroscopic data for several dinuclear Pd(II) complexes, including the precursor {[Pd(dppH)(μ-Cl)]}₂ and multiple decomposition products of the sensitive compounds [Pd(dpp)(PnPh₃)].

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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.