Communication
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amount of copper). On this basis, and due to the data obtained
from recycling experiments, we can be confident the material is not
a supplier of a homogenous catalyst species for the reaction.
Additional evidence for this conclusion comes from additional
catalytic experiments we have briefly investigated, namely ‘‘click
chemistry’’ and hydrosilylation reactions, where we observed that
the MOF does not catalyse these reactions. This observation we
attribute to increased molecular size of the reactants involved and
heterogeneous nature of this MOF catalyst.
In conclusion, we have reported the first example of a MOF
comprising a Cu(I) bis-NHC ligand catalytic site. This entity is
formed in situ from an azolium ligand and a Cu(I) source. The
‘pairing’ of ligands in the MOF generates an unusual Zn4O SBU and
a structurally flexible diamondoid 3D network. As the Cu(I) bis-NHC
site is a structural building block the catalytic sites are well defined
and the MOF shows similar catalytic behaviour to related homo-
genous Cu(I) NHC species yet has the advantage of being a hetero-
geneous system that can be recovered following a reaction. Our
results show for the first time that catalysis by bis-NHC species
within a MOF is possible however, a more robust framework will be
required to realise the full potential of these moieties.
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This research is supported by the Science and Industry
Endowment Fund (SIEF). CJD and CJS would like to acknowledge
the Australian Research Council for funding FT100100400 and
FT0991910, respectively.
Notes and references
‡ In some instances MOFs are known to catalyse reactions via dissolu-
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systems, we cannot entirely rule out the presence of a highly active
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