Solvent-Induced Spin-State Change in Copper Corroles
Solvent-Induced Spin-State Change in Copper Corroles
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DOI：
10.1021/acs.inorgchem.2c02678
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发表时间：
2022-12-02
影响因子：
4.6
通讯作者：
Nocera，Daniel G.
中科院分区：
文献类型：
--
作者：
Lemon，Christopher M.;Maher，Andrew G.;Nocera，Daniel G.
自咔咯化学问世以来，铜咔咯的电子结构一直是一个争论和修正的话题。这些化合物的基态是最好的描述为一个反铁磁耦合铜（II）咔咯自由基阳离子。在配位溶剂中，这些分子变得顺磁性，并且这通常伴随着颜色变化。这些溶剂诱导性质的基本化学性质目前尚不清楚。在这里，我们表明，一个协调的溶剂，如吡啶，诱导从反铁磁耦合的Cu（II）corrole自由基阳离子的铁磁耦合的三重态在地面自旋状态的变化。随着时间的推移，三重态反应产生一种具有单电子还原Cu（II）咔咯特征的光谱特征的物质。这些观察占溶剂诱导的顺磁性和相关的颜色变化，已观察到的铜corroles在协调溶剂。
The electronic structure of copper corroles has been a topic of debate and revision since the advent of corrole chemistry. The ground state of these compounds is best described as an antiferromagnetically coupled Cu(II) corrole radical cation. In coordinating solvents, these molecules become paramagnetic, and this is often accompanied by a color change. The underlying chemistry of these solvent-induced properties is currently unknown. Here, we show that a coordinating solvent, such as pyridine, induces a change in the ground spin state from an antiferromagnetically coupled Cu(II) corrole radical cation to a ferromagnetically coupled triplet. Over time, the triplet reacts to produce a species with spectral signatures that are characteristic of the one-electron-reduced Cu(II) corrole. These observations account for the solvent-induced paramagnetism and the associated color changes that have been observed for copper corroles in coordinating solvents.