Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks

William Morris, Boris Volosskiy, Selcuk Demir, Felipe Gándara, Psaras L. McGrier, Hiroyasu Furukawa, Duilio Cascio, J. Fraser Stoddart, and Omar M. Yaghi, Inorg. Chem., 2012, 51 (12), pp 6443–6445 DOI: 10.1021/ic300825s

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Abstract: Three new metal–organic frameworks [MOF-525, Zr6O4(OH)4(TCPP-H2)3; MOF-535, Zr6O4(OH)4(XF)3; MOF-545, Zr6O8(H2O)8(TCPP-H2)2, where porphyrin H4-TCPP-H2 = (C48H24O8N4) and cruciform H4-XF = (C42O8H22)] based on two new topologies, ftw and csq, have been synthesized and structurally characterized. MOF-525 and -535 are composed of Zr6O4(OH)4 cuboctahedral units linked by either porphyrin (MOF-525) or cruciform (MOF-535). Another zirconium-containing unit, Zr6O8(H2O)8, is linked by porphyrin to give the MOF-545 structure. The structure of MOF-525 was obtained by analysis of powder X-ray diffraction data. The structures of MOF-535 and -545 were resolved from synchrotron single-crystal data. MOF-525, -535, and -545 have Brunauer–Emmett–Teller surface areas of 2620, 1120, and 2260 m2/g, respectively. In addition to their large surface areas, both porphyrin-containing MOFs are exceptionally chemically stable, maintaining their structures under aqueous and organic conditions. MOF-525 and -545 were metalated with iron(III) and copper(II) to yield the metalated analogues without losing their high surface area and chemical stability.

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