Meiyuan Guo, Robert Temperton, Giulio D’Acunto, Niclas Johansson, Rosemary Jones, Karsten Handrup, Sven Ringelband, Om Prakash, Hao Fan, Lisa H. M. de Groot, Valtýr Freyr Hlynsson, Simon Kaufhold, Olga Gordivska, Nicolás Velásquez González, Kenneth Wärnmark, Joachim Schnadt, Petter Persson and Jens Uhlig*,
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引用次数: 0
Abstract
Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.
The measurement and advanced modeling of soft X-ray absorption spectra from both the ligand and the metal center allowed a unique view of the orbitals inside complex molecules and the extraction of descriptive parameters.
近年来,以铁为中心的 N-heterocyclic carbene 化合物因其具有电荷转移(CT)特性的长寿命激发态而备受关注。了解金属与配体轨道之间的相互作用对于合理调整过渡金属化合物的性质(例如未来的光伏和光催化应用)具有重要意义。在此,我们利用铁 L 边和氮 K 边 X 射线吸收光谱(XAS)研究了一系列中心铁离子氧化态为 +2、+3 和 +4 的铁中心 N-杂环碳烯配合物。通过受限活动空间(RAS)和多重计算模拟和解释了铁 L 边 XAS 实验数据。通过时间相关密度泛函理论(TDDFT)计算,模拟并比较了 N K 边 XAS 实验数据。通过结合互补的 Fe L-edge 和 N K-edge XAS,可以直接探测金属和配体特征轨道的复杂相互作用。对不同配体的 σ 供能和 π 受能进行了比较、评估和讨论。研究结果表明,X 射线光谱与先进的建模相结合,可以成为了解金属和配体复杂相互作用的有力工具。
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.