Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework

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-r...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2019-10, Vol.141 (42), p.16884-16893
Main Authors: Jiang, Yi, Oh, Inseon, Joo, Se Hun, Buyukcakir, Onur, Chen, Xiong, Lee, Sun Hwa, Huang, Ming, Seong, Won Kyung, Kwak, Sang Kyu, Yoo, Jung-Woo, Ruoff, Rodney S
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Language:English
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Summary: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).
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b08601