可逆电子转移及伴随自组装形成的镱-吡嗪方阵[(C5H4Me)2YbIII(pyz•-)]4。

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-07-28 Epub Date: 2025-07-16 DOI:10.1021/acs.inorgchem.5c02655

Himanshu Gupta, Asmita Sen, Patrick W Smith, Brett D Vincenzini, Niki Mavragani, Dumitru-Claudiu Sergentu, Alexandra M Bacon, Corwin H Booth, Muralee Murugesu, Stefan G Minasian, Jochen Autschbach, Eric J Schelter

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引用次数: 0

摘要

吡嗪（Pyrazine, pyz）在配位化学中被广泛应用于混合价化合物和强偶联材料的电子离域。本研究以YbII前体[(C5H4Me)2YbII(THF)2](1)为原料，利用金属-配体氧化还原协同作用合成了分子方[(C5H4Me)2YbIII(pyz•-)]4·1/2(C7H5F3)(2)。在一系列的研究中，包括结构分析、磁强计、振动光谱、x射线吸收近边缘结构光谱和电子结构计算，配合物2显示了从YbII到吡嗪的电荷转移的证据。DFT计算支持在紫外-可见光谱中的低能带分配为吡嗪- somo -金属-4f电荷转移。磁性研究表明，自由基桥接yb -方配合物的Yb-pyz•-交换偶联为-3.6 cm-1， pyz•- pyz•-偶联为-18.6 cm-1。

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An Ytterbium-Pyrazine Square [(C₅H₄Me)₂Yb^III(pyz^•-)]₄ Formed by Reversible Electron Transfer and Concomitant Self-Assembly.

Pyrazine (pyz) has been used extensively in coordination chemistry to manifest electron delocalization in mixed-valent compounds and strongly coupled materials. In the current work, using a Yb^II precursor, [(C₅H₄Me)₂Yb^II(THF)₂] (1), a molecular square [(C₅H₄Me)₂Yb^III(pyz^•-)]₄·¹/₂(C₇H₅F₃) (2) was synthesized by metal-ligand redox cooperativity. Complex 2 shows evidence of charge transfer from Yb^II to pyrazine in a range of studies including structural analysis, magnetometry, vibrational spectroscopy, X-ray absorption near-edge structure spectroscopy, and electronic structure calculations. DFT calculations support the assignment of low-energy bands in the UV-vis spectrum as pyrazine-SOMO-to-metal-4f charge transfer. Magnetic studies reveal a Yb-pyz^•- exchange coupling of -3.6 cm^-1 and pyz^•--pyz^•- coupling of -18.6 cm^-1 for the radical bridged Yb-square complex.

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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.