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

William Morris(University of California, Los Angeles), Boris Volosskiy(University of California, Los Angeles), Selçuk Demir(University of California, Los Angeles), Felipe Gándara(University of California, Los Angeles), Psaras L. McGrier(Northwestern University), Hiroyasu Furukawa(University of California, Los Angeles), Duilio Cascio(University of California, Los Angeles), J. Fraser Stoddart(Northwestern University), Omar M. Yaghi(Lawrence Berkeley National Laboratory)
Inorganic Chemistry
June 7, 2012
10.1021/ic300825s
Cited by 892

Abstract

Three new metal-organic frameworks [MOF-525, Zr(6)O(4)(OH)(4)(TCPP-H(2))(3); MOF-535, Zr(6)O(4)(OH)(4)(XF)(3); MOF-545, Zr(6)O(8)(H(2)O)(8)(TCPP-H(2))(2), where porphyrin H(4)-TCPP-H(2) = (C(48)H(24)O(8)N(4)) and cruciform H(4)-XF = (C(42)O(8)H(22))] based on two new topologies, ftw and csq, have been synthesized and structurally characterized. MOF-525 and -535 are composed of Zr(6)O(4)(OH)(4) cuboctahedral units linked by either porphyrin (MOF-525) or cruciform (MOF-535). Another zirconium-containing unit, Zr(6)O(8)(H(2)O)(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 m(2)/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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