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Structures, sorption, separation and magnetic properties of metalloligund-based metal-organic frameworks 원문보기

  • 저자

    유대원

  • 학위수여기관

    Graduate School, Korea University

  • 학위구분

    국내박사

  • 학과

    化學科

  • 지도교수

    洪昌燮

  • 발행년도

    2014

  • 총페이지

    ix, 117장

  • 키워드

    Metal-Organic Framework magnetism chiral separation gas adsorption;

  • 언어

    eng

  • 원문 URL

    http://www.riss.kr/link?id=T13541882&outLink=K  

  • 초록

    Magnetic metal organic frameworks (MOFs) have become one of current subjects because they carry magnetic and sorptive properties at the same time. However, magnetic coupling frequently demands a short bridging pathway between magnetic centers, while porosity is commonly formed from a long bridging ligand. Therefore, one needs to develop an elaborated synthetic strategy to fulfill this antagonistic requirement. In this regard, we have used a paramagnetic metalloligand with exodentate sites serving as binding positions towards incoming magnetic metal ions. In part II, We have prepared a 3-D porous bimetallic material, [Cu(Tt)2][Mn(salen)]2(ClO4)2∙7H2O [Tt = tris(triazoyl)borate, salen = N,N'-ethylenebis(salicylideneiminato) dianion] constructed from metalloligands Cu(Tt)2 with six additional coordination sites. Dehydration of the three-dimensional Cu(II)-Mn(III) coordination network undergoes a dramatic magnetic phase transformation from a paramagnetic state to a long-range magnetic ordered phase with glassy behavior. The gas adsorption behavior and re-entrant spin glass character are uniquely apparent in the dehydrated sample. In part III, a porous 3D framework, [Co(Tt)2][Cu6(ip)6]∙7DMF∙3H2O, was synthesized by a solvothermal reaction. Single crystal structure contains copper paddle-wheel secondary building unit (SBU). Each SBU is connected to nearby SBUs through metalloligands. The Co(II)-Cu(II) framework shows a permanent porosity with a high surface area for magnetic MOFs as well as a magnetic interaction upon solvation-desolvation and exchanging the solvent. The most effective strategy to construct chiral MOFs is to use chiral ligands as building blocks or linkers. Among chiral ligands, camphoric acid has constructed a variety of chiral MOFs of transition metals. In part IV, two MOFs are synthesized by the interplay of both the metalloligand and camphoric acid which have enabled us not only to direct their selective separation of chiral 1-phenylethanol but also to show antiferromagnetic property. Detailed structures, sorption, separation and magnetic properties were described.


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