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Metal‐Ion Metathesis in Metal–Organic Frameworks: A Synthetic Route to New Metal–Organic Frameworks
Authors:Yonghwi Kim  Dr Sunirban Das  Saurav Bhattacharya  Soonsang Hong  Dr Min Gyu Kim  Dr Minyoung Yoon  Prof Dr Srinivasan Natarajan  Prof Dr Kimoon Kim
Institution:1. Center for Smart Supramolecules, Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology, San 31 Hyojadong, Pohang 790‐784 (Korea), Fax: (+82)?54‐279‐8129;2. Framework Solids laboratory Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore‐560012 (India);3. Pohang Accelerator Laboratory (PAL), Pohang University of Science and Technology, San 31 Hyojadong, Pohang 790‐784 (Korea)
Abstract:A porous metal–organic framework, Mn(H3O)(Mn4Cl)3(hmtt)8] (POST‐65), was prepared by the reaction of 5,5′,10,10′,15,15′‐hexamethyltruxene‐2,7,12‐tricarboxylic acid (H3hmtt) with MnCl2 under solvothermal conditions. POST‐65(Mn) was subjected to post‐synthetic modification with Fe, Co, Ni, and Cu according to an ion‐exchange method that resulted in the formation of three isomorphous frameworks, POST‐65(Co/Ni/Cu), as well as a new framework, POST‐65(Fe). The ion‐exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasma–atomic emission spectrometry (ICP‐AES), powder X‐ray diffraction (PXRD), and Brunauer–Emmett–Teller (BET) surface‐area analysis. Single‐crystal X‐ray diffractions studies revealed a single‐crystal‐to‐single‐crystal (SCSC)‐transformation nature of the ion‐exchange process. Hydrogen‐sorption and magnetization measurements showed metal‐specific properties of POST‐65.
Keywords:adsorption  magnetism  metal‐ion exchange  metal–  organic frameworks  metathesis
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