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

Journal Article · Wed Oct 24 00:00:00 EDT 2012 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic300825s· OSTI ID:1048569

Morris, William; Volosskiy, Boris; Demir, Selcuk; Gándara, Felipe; McGrier, Psaras L; Furukawa, Hiroyasu; Cascio, Duilio; Stoddart, J Fraser; Yaghi, Omar M ^[1]

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1. UCLA

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.

• Research Organization: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
• Sponsoring Organization: NSFOTHERDOE - BASIC ENERGY SCIENCESINDUSTRY
• OSTI ID: 1048569
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: (12) ; 06, 2012 Vol. 51; ISSN 0020-1669; ISSN INOCAJ
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
PORPHYRINS
STABILITY
SURFACE AREA
SYNCHROTRONS
SYNTHESIS
X-RAY DIFFRACTION
ZIRCONIUM