Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework,Journal of the American Chemical Society

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Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-10-14 , DOI: 10.1021/jacs.9b08601
Yi Jiang ₁ , Inseon Oh ₂ , Se Hun Joo ₃ , Onur Buyukcakir ₁ , Xiong Chen ₁ , Sun Hwa Lee ₁ , Ming Huang ₁ , Won Kyung Seong ₁ , Sang Kyu Kwak ₃ , Jung-Woo Yoo ₂ , Rodney S Ruoff _{1,

2,

3,

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Affiliation

We report the synthesis and characterization of a two-dimensional (2D) conjugated Ni(II) tetraaza[14]annulene-linked metal organic framework (NiTAA-MOF) where NiTAA is a macrocyclic MN4 (M = metal, N = nitrogen) compound. The structure of NiTAA-MOF was elucidated by Fourier-transform infrared, X-ray photoemission, and X-ray diffraction spectroscopies, in combination with density functional theory (DFT) calculations. When chemically oxidized by iodine, the insulating bulk NiTAA-MOF (σ < 10-10 S/cm) exhibits an electrical conductivity of 0.01 S/cm at 300 K, demonstrating the vital role of ligand oxidation in the electrical conductivity of 2D MOFs. Magnetization measurements show that iodine-doped NiTAA-MOF is paramagnetic with weak antiferromagnetic coupling due to the presence of organic radicals of oxidized ligands and high-spin Ni(II) sites of the missing-linker defects. In addition to providing further insights into the origin of the induced electrical conductivity in 2D MOFs, both pristine and iodine-doped NiTAA-MOF synthesized in this work could find potential applications in areas such as catalase mimics, catalysis, energy storage, and dynamic nuclear polarization-nuclear magnetic resonance (DNP-NMR).

中文翻译：

Ni(II)四氮杂[14]环烯连接的金属有机骨架中的部分氧化诱导的导电性和顺磁性

我们报告了二维 (2D) 共轭 Ni(II) 四氮杂 [14] 环烯连接的金属有机骨架 (NiTAA-MOF) 的合成和表征，其中 NiTAA 是大环 MN4（M = 金属，N = 氮）化合物. NiTAA-MOF 的结构通过傅里叶变换红外光谱、X 射线光电发射和 X 射线衍射光谱结合密度泛函理论 (DFT) 计算阐明。当被碘化学氧化时，绝缘体 NiTAA-MOF (σ < 10-10 S/cm) 在 300 K 下表现出 0.01 S/cm 的电导率，表明配体氧化在 2D MOF 电导率中的重要作用。磁化测量表明，由于氧化配体的有机自由基和缺失接头缺陷的高自旋 Ni(II) 位点的存在，碘掺杂的 NiTAA-MOF 具有弱反铁磁耦合的顺磁性。除了提供对 2D MOF 中感应电导率起源的进一步了解之外，在这项工作中合成的原始和碘掺杂的 NiTAA-MOF 都可以在过氧化氢酶模拟、催化、能量存储和动态核等领域找到潜在的应用。极化核磁共振（DNP-NMR）。

更新日期：2019-10-14

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