A R T I C L E S
Li et al.
already been utilized directly as precursors for the preparation
of MOFs.11j,18
In this work, we propose that the use of the quadruply bonded
Mo-Mo dinuclear unit Mo2(O2C-)4 as a structural base will
enable construction of molecular metal-organic assemblies
amenable to study in solution by methods such as UV-vis,
NMR, and CV. The introduction of metal-metal bonded clusters
into molecular assemblies was pioneered by Cotton and
Chisholm.12,13 While other groups also reported a few interesting
molecular assembles containing similar metal-metal bonded
clusters during that time and thereafter,14 including our own
cuboctahedral and anti-cuboctahedral cages,15 very few Mo-Mo
cluster-containing supramolecular polyhedral cages13a have been
investigated before this work.
To expand this fascinating chemistry, herein we report a
systematic study on the construction of molecular metal-organic
architectures with quadruply bonded Mo-Mo dimers and 12
angular dicarboxylate ligands. The quadruply bonded Mo-Mo
paddlewheel unit in the form of Mo2(O2CR)4 is robust and can
be preserved in the molecular assemblies. Four carboxylates
surround each paddlewheel to form a square unit. Linkage from
Mining of the inorganic small-molecule library reveals an
enormous range of multimetal entities (e.g. multinuclear metal
carboxylates) potentially adoptable as nodes for the construction
of diverse molecular architectures. An additional advantage of
using multimetal nodes comes from the inclusion of their
inherent properties, such as stability and magnetism, into the
supramolecular systems, resulting in additional interesting
properties and functions. These characteristics can widen the
spectrum of metal-containing supramolecular chemistry.
Most multimetal node-based molecular polygonal and poly-
hedral architectures reported contain the paddlewheel
Cu2(O2C-)4 structural unit, likely because of the ease of
preparation; however, these are difficult to study in solution.11
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