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M(ii) (M = Mn, Co, Ni) variants of the MIL-53-type structure with pyridine-N-oxide as a co-ligand

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Munn, Alexis S., Clarkson, Guy J., Millange, Franck, Dumont, Yves and Walton, Richard I. (2013) M(ii) (M = Mn, Co, Ni) variants of the MIL-53-type structure with pyridine-N-oxide as a co-ligand. CrystEngComm, Volume 15 (Number 45). pp. 9679-9687. doi:10.1039/c3ce41268g ISSN 1466-8033.

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Official URL: http://dx.doi.org/10.1039/c3ce41268g

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Abstract

The synthesis and structures of metal–organic framework materials with three-dimensional structures related to the well-known MIL-53 framework are described. These have general chemical formula M(BDC)(PNO), where BDC = 1,4-benzenedicarboxylate, PNO = pyridine-N-oxide, and M = Mn, Co or Ni. The materials contain infinite chains of octahedral metal centres connected by trans corner sharing and cross-linked by 1,4-benzenedicarboxylate anions, where the bridging oxygen atoms in the inorganic chains belong to pyridine-N-oxide ligands. The pyridine rings of these additional ligands project into the extra-framework space, rendering the structure non-porous. The metal ions are present in the +2 oxidation state, as verified using XANES spectroscopy for the case of M = Co. Solid solutions M11−xM2x(BDC)(PNO) can be prepared, which is confirmed using high resolution powder X-ray diffraction. Magnetic susceptibility measurements show antiferromagnetic behaviour at low temperatures for M = Ni or Mn, whereas for M = Co there is evidence for low temperature ferromagnetic interactions. The mean effective magnetic moments deduced per metal ion are consistent with the +2 oxidation states in octahedral coordination.

Item Type: Journal Article
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Journal or Publication Title: CrystEngComm
Publisher: Royal Society of Chemistry
ISSN: 1466-8033
Official Date: 2013
Dates:
DateEvent
2013Published
Volume: Volume 15
Number: Number 45
Page Range: pp. 9679-9687
DOI: 10.1039/c3ce41268g
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access

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