Dual-Channel-Mediated Spin Coupling for One-Electron-Oxidized Cobalt(II)-Saddled Porphyrin

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• 作者：Ru-Jen Cheng ; Yu-Hsuan Chen ; Ching-Chin Chen ; Gene-Hsiang Lee ; Shie-Ming Peng ; Peter Ping-Yu Chen
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：September 2, 2014
• 年：2014
• 卷：53
• 期：17
• 页码：8848-8850
• 全文大小：181K
• ISSN：1520-510X

文摘

Saddle-shaped Co^II[OET(p-R)PP] (R = CF₃, H, CH₃) can be readily oxidized with Cl₂, Br₂, and I₂ to the corresponding one-electron-oxidation product Co[OET(p-R)PP]X (X = Cl, Br, I) with the clear character of a ring cation radical. With the series of ¹H and ¹³C NMR spectra of these related complexes, both the axial ligand and peripheral substituent of the ring macrocycle are proven to act as a dual channel to tune spin coupling between low-spin Co(II) and a porphyrin 蟺-cation radical. Density functional theory calculations have shown that the antiferromagnetic coupling between spins residing in d_z² and a_2u are expected to exist as the ground state. The paramagnetic properties are attributed to an a_1u-type ferromagnetic excited triplet state.