TY - JOUR
T1 - Ligand Redox Non-innocence in the Stoichiometric Oxidation of Mn2(2,5-dioxidoterephthalate) (Mn-MOF-74)
AU - Cozzolino, Anthony
AU - Brozek, Carl K
AU - Palmer, Ryan D
AU - Yano, Junko
AU - Li, Minyuan
AU - Dinca, Mircea
PY - 2014/3/5
Y1 - 2014/3/5
N2 - We demonstrate that unsaturated metal sites
within the nodes of metal‐organic frameworks can be inter‐
rogated by redox reagents common to small molecule chem‐
istry. We show, for the first time, that an analogue of the
iconic M2(2,5‐dioxidoterephthalate) (M2DOBDC, MOF‐74)
class of materials can be stoichiometrically oxidized by one
electron per metal center. The reaction of Mn2DOBDC with
the hypervalent iodine reagent iodobenzene dichloride,
PhICl2, requires precise control of both stoichiometry and
temperature to produce the oxidized material
Cl2Mn2DOBDC, which retains crystallinity and porosity. This
contrasts with oxidations by Cl2 and other gaseous oxidants,
which cause decomposition of the parent framework. Sur‐
prisingly, magnetic measurements, X‐ray absorption and
infrared spectroscopic data show that the Mn ions maintain a
formal oxidation state of +2, suggesting instead the oxidation
of the DOBDC4
ligand to the quinone DOBDC2
. Control
expe
AB - We demonstrate that unsaturated metal sites
within the nodes of metal‐organic frameworks can be inter‐
rogated by redox reagents common to small molecule chem‐
istry. We show, for the first time, that an analogue of the
iconic M2(2,5‐dioxidoterephthalate) (M2DOBDC, MOF‐74)
class of materials can be stoichiometrically oxidized by one
electron per metal center. The reaction of Mn2DOBDC with
the hypervalent iodine reagent iodobenzene dichloride,
PhICl2, requires precise control of both stoichiometry and
temperature to produce the oxidized material
Cl2Mn2DOBDC, which retains crystallinity and porosity. This
contrasts with oxidations by Cl2 and other gaseous oxidants,
which cause decomposition of the parent framework. Sur‐
prisingly, magnetic measurements, X‐ray absorption and
infrared spectroscopic data show that the Mn ions maintain a
formal oxidation state of +2, suggesting instead the oxidation
of the DOBDC4
ligand to the quinone DOBDC2
. Control
expe
M3 - Article
SN - 0002-7863
SP - 3334
EP - 3337
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -