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제125회 대한화학회 학술발표회 및 총회 Thermally Reduced Radical Anionic Metal-Organic Framework

2020년 2월 13일 13시 25분 25초
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Inorganic Chemistry
저자 및
Seonghun Park, Jinhee Park1,*
Emerging Materials Science, Daegu Gyeongbuk Institute of Science & Technology, Korea
1Department of Emerging Materials Science, Daegu Gyeongbuk Institute of Science & Technology, Korea
Metal-organic frameworks (MOFs) are a class of robust, highly porous, crystalline organic-inorganic hybrid materials that have received tremendous attention due to their designability, tunability, and well-ordered porous structures. Herein, we report thermally regulated formation of a radical anionic MOF consisting of an electron-withdrawing 1,4,5,8-naphthalenediimide (NDI) based carboxylate ligand and Nd3+. Interestingly, the ligand was reduced to the radical anionic state during the solvothermal synthesis, resulting in the formation of radical anionic MOF. The exposure to air, expecially O2, oxidized the MOF into the neutral one which can be re-reduced by heat treatment. This process was reversible at least for 5 times. The reduction into the radical anionic MOF depends on the duration and temperature of the heat treatment. The radical anionic state was maintained for 1 month under inert conditions, which is revealed by the electron paramagnetic resonance (EPR) analysis. Notably, during the reduction process, the coordinated, disordered DMF becomes ordered implying that the DMF is the electron donor for the thermal reduction of MOFs. This study presents the new facile method to generate radical anionic MOFs.