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@ARTICLE{Breeze:167766,
      author       = {Breeze, Matthew I. and Clet, Guillaume and Campo, Betiana
                      C. and Vimont, Alexandre and Daturi, Marco and Grenèche,
                      Jean-Marc and Dent, Andrew J. and Millange, Franck and
                      Walton, Richard},
      title        = {{I}somorphous {S}ubstitution in a {F}lexible
                      {M}etal–{O}rganic {F}ramework: {M}ixed-{M}etal,
                      {M}ixed-{V}alent {MIL}-53 {T}ype {M}aterials},
      journal      = {Inorganic chemistry},
      volume       = {52},
      number       = {14},
      issn         = {1520-510X},
      address      = {Washington, DC},
      publisher    = {American Chemical Society},
      reportid     = {DESY-2014-02097},
      pages        = {8171 - 8182},
      year         = {2013},
      note         = {© American Chemical Society},
      abstract     = {Mixed-metal iron–vanadium analogues of the
                      1,4-benzenedicarboxylate (BDC) metal–organic framework
                      MIL-53 have been synthesized solvothermally in
                      N,N′-dimethylformamide (DMF) from metal chlorides using
                      initial Fe:V ratios of 2:1 and 1:1. At 200 °C and short
                      reaction time (1 h), materials (Fe,V)II/IIIBDC(DMF1–xFx)
                      crystallize directly, whereas the use of longer reaction
                      times (3 days) at 170 °C yields phases of composition
                      [(Fe,V)III0.5(Fe,V)0.5II(BDC)(OH,F)]0.5–·0.5DMA+ (DMA =
                      dimethylammonium). The identity of the materials is
                      confirmed using high-resolution powder X-ray diffraction,
                      with refined unit cell parameters compared to known pure
                      iron analogues of the same phases. The oxidation states of
                      iron and vanadium in all samples are verified using X-ray
                      absorption near edge structure (XANES) spectroscopy at the
                      metal K-edges. This shows that in the two sets of materials
                      each of the vanadium and the iron centers are present in
                      both +2 and +3 oxidation states. The local environment and
                      oxidation state of iron is confirmed by 57Fe Mössbauer
                      spectrometry. Infrared and Raman spectroscopies as a
                      function of temperature allowed the conditions for removal
                      of extra-framework species to be identified, and the
                      evolution of μ2-hydroxyls to be monitored. Thus calcination
                      of the mixed-valent, mixed-metal phases
                      [(Fe,V)III0.5(Fe,V)0.5II(BDC)(OH,F)]0.5–·0.5DMA+ yields
                      single-phase MIL-53-type materials, (Fe,V)III(BDC)(OH,F).
                      The iron-rich, mixed-metal MIL-53 shows structural
                      flexibility that is distinct from either the pure Fe
                      material or the pure V material, with a thermally induced
                      pore opening upon heating that is reversible upon cooling.
                      In contrast, the material with a Fe:V content of 1:1 shows
                      an irreversible expansion upon heating, akin to the pure
                      vanadium analogue, suggesting the presence of some domains
                      of vanadium-rich regions that can be permanently oxidized to
                      V(IV).},
      cin          = {DOOR},
      ddc          = {540},
      cid          = {I:(DE-H253)HAS-User-20120731},
      pnm          = {DORIS Beamline F3 (POF2-54G13)},
      pid          = {G:(DE-H253)POF2-F3-20130405},
      experiment   = {EXP:(DE-H253)D-F3-20150101},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000322087100041},
      pubmed       = {pmid:23815225},
      doi          = {10.1021/ic400923d},
      url          = {https://bib-pubdb1.desy.de/record/167766},
}