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Ferromagnetic Coupling in Oxidovanadium(IV)–Porphyrin Radical Dimers
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-10-19 , DOI: 10.1021/acs.inorgchem.1c02331 Akhil Kumar Singh 1 , Mohammad Usman 1 , Sabyasachi Sarkar 1 , Giuseppe Sciortino 2, 3 , Devesh Kumar 4 , Eugenio Garribba 2 , Sankar Prasad Rath 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-10-19 , DOI: 10.1021/acs.inorgchem.1c02331 Akhil Kumar Singh 1 , Mohammad Usman 1 , Sabyasachi Sarkar 1 , Giuseppe Sciortino 2, 3 , Devesh Kumar 4 , Eugenio Garribba 2 , Sankar Prasad Rath 1
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Three different oxidovanadium(IV) porphyrin dimers with anti, cis, and trans arrangements of the two rings have been synthesized by changing the bridge between the porphyrin macrocycles. This provides a unique opportunity to investigate the role of the bridge and spatial arrangement between the two VIVO centers for their electronic communication and magnetic coupling. They were characterized by the combined application of XRD analysis, UV–vis and electron paramagnetic resonance (EPR) spectroscopy, cyclic voltammetry, magnetic susceptibility, and DFT calculations. One- and two-electron oxidations produce mono- and dication diradical species, respectively, which display an unusual ferromagnetic interaction between the unpaired spins of vanadium(IV) and porphyrin π-cation radical, in contrast to other metalloporphyrin dimers. The oxidized species show a dissimilar behavior between cis and trans isomers. The ferromagnetic coupling occurs between the porphyrin π-cation radical and the unpaired electron of the VIVO ion on the dxy orbital, orthogonal to the porphyrin-based molecular orbitals a1u and a2u.
中文翻译：
氧化钒 (IV)-卟啉自由基二聚体中的铁磁耦合
通过改变卟啉大环之间的桥，合成了三个不同的氧化钒 (IV) 卟啉二聚体，两个环具有反、顺和反式排列。这提供了一个独特的机会来研究桥梁的作用和两个 V IV之间的空间安排O 中心为他们的电子通讯和磁耦合。它们通过 XRD 分析、UV-vis 和电子顺磁共振 (EPR) 光谱、循环伏安法、磁化率和 DFT 计算的组合应用进行表征。单电子和双电子氧化分别产生单和双阳离子双自由基物质，与其他金属卟啉二聚体相比，钒 (IV) 和卟啉 π 阳离子自由基的未配对自旋之间显示出不寻常的铁磁相互作用。氧化物质在顺式和反式异构体之间表现出不同的行为。卟啉π-阳离子自由基与d xy上V IV O 离子的未成对电子之间发生铁磁耦合轨道，正交于基于卟啉的分子轨道 a 1u和 a 2u。
更新日期：2021-11-01
中文翻译：
氧化钒 (IV)-卟啉自由基二聚体中的铁磁耦合
通过改变卟啉大环之间的桥，合成了三个不同的氧化钒 (IV) 卟啉二聚体，两个环具有反、顺和反式排列。这提供了一个独特的机会来研究桥梁的作用和两个 V IV之间的空间安排O 中心为他们的电子通讯和磁耦合。它们通过 XRD 分析、UV-vis 和电子顺磁共振 (EPR) 光谱、循环伏安法、磁化率和 DFT 计算的组合应用进行表征。单电子和双电子氧化分别产生单和双阳离子双自由基物质，与其他金属卟啉二聚体相比，钒 (IV) 和卟啉 π 阳离子自由基的未配对自旋之间显示出不寻常的铁磁相互作用。氧化物质在顺式和反式异构体之间表现出不同的行为。卟啉π-阳离子自由基与d xy上V IV O 离子的未成对电子之间发生铁磁耦合轨道，正交于基于卟啉的分子轨道 a 1u和 a 2u。
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