有机金属配合物的合成、光物理性质和光学限制行为:金属中心和共轭二亚胺配体的影响

IF 2.2 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR European Journal of Inorganic Chemistry Pub Date : 2024-10-24 DOI:10.1002/ejic.202400460
Chenglong Wu, Yongqi Bao, Guihong Ren, Chenyi Wang, Senqiang Zhu, Rui Liu, Hongjun Zhu
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引用次数: 0

摘要

合成了四种具有相同共轭二亚胺配体和不同过渡金属中心(Rh(III), Ir(III), Ru(II)和Os(II))的有机金属配合物。通过紫外-可见吸收、发射、瞬态吸收(TA)光谱以及光功率限制(OPL)测量,对这些配合物及其相应的二亚胺配体的光物理性质进行了全面的研究。芴组分与烷基链的掺入增强了配体的π-共轭作用,防止了分子间π-π堆积,提高了配合物的溶解度。二亚胺配体的发射光谱显示出轻微的溶剂化效应,表明其发射态的主要性质是分子内电荷转移(CT)。根据这四种配合物的价态,可将它们分为两类(Rh(III), Ir(III))和(Ru(II), Os(II))。对于TA光谱,前者在400~800 nm范围内呈现出正的ΔOD值,而后者在420~500 nm范围内由于基态吸收显著,呈现出大的倒置峰。此外,配合物的光限制行为为:1 d>;1 a>1 c>1 b。配合物1d在532 nm处表现出强大的反向饱和吸收(RSA)特性,可以作为一种很好的非线性吸收材料。
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Synthesis, Photophysical Properties and Optical Limiting Behavior of Organometallic Complexes: Influence of Metal Centers and Conjugated Diimine Ligands

Four organometallic complexes featuring identical conjugated diimine ligands and varying transition metal centers (Rh(III), Ir(III), Ru(II), and Os(II)) were synthesized. A comprehensive investigation of the photophysical properties of these complexes and their corresponding diimine ligands was conducted by UV-vis absorption, emission, and transient absorption (TA) spectroscopy, as well as optical power limiting (OPL) measurements. The incorporation of fluorene components with alkyl chains enhanced the π-conjugation of the ligand, prevented intermolecular π-π stacking, and improved complex solubility. The diimine ligands showed a slight solvation effect in their emission spectra, indicating that the main property of their emissive state was intramolecular charge transfer (CT). According to the valence states of the four complexes, they can be divided into two classes (Rh(III), Ir(III)) and (Ru(II), Os(II)). For TA spectrum, the former group exhibited positive ΔOD values across the 400~800 nm range, while the latter showed large inverted peaks at 420~500 nm due to significant ground-state absorption in this wavelength range. Additionally, the optical limiting conduct of the complexes observed the order: 1 d>1 a>1 c>1 b. Complex 1 d exhibits powerful reverse saturable absorption (RSA) properties at 532 nm and could probably be used as an wonderful nonlinear absorbing material.

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来源期刊
European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
4.30
自引率
4.30%
发文量
419
审稿时长
1.3 months
期刊介绍: The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.
期刊最新文献
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