With the principles of reticular chemistry, metal-organic frameworks (MOFs)
with enhanced storage and catalytic capabilities have been prepared. This dissertation
presents the synthesis of azo-IRMOF-74-III for controllable release of cargo
molecules as well as the catalytic testing of MOF-525-Mn and an isoreticular series
of MOFs based on the MOF-5 framework. The variation of pore metrics in
these frameworks show the versatility of reticular chemistry and their application
in catalytic reactions.
First, an azobenzene containing MOF-74 analogue was prepared by incorporating
the azobenezne moiety into the organic linker used to prepare MOF-74.
Cargo molecules were trapped inside the structure based on size constraints and
controllably released via modulation of UV irradiation to induce a trans to cis
isomerization on the organic linker. The variation in the linker lengh shows that
specic cargo molecules can be trapped by changing the size of the one-dimensional
pore in reticular frameworks.
In addition to changing pore size, density of catalytic sites inside a pore was
investigated through the isoreticular synthesis of a series of MOFs, modeled after MOF-5 but containing various amounts of 2-aminoterephthalic acid. These amine
groups were post-synthetically modied to contain catalytically active Pd sites and
heterogeneous Heck coupling was performed. A inverse relationship was observed
between the amount of framework metalation and reaction yield and selectivity.
This is attributed to pore blocking from post-synthetic modication at higher
metal loadings.
Finally, a manganese porphyrin containing MOF, MOF-525-Mn, was synthesized
and its activity tested through the epoxidation of alkenes using molecular
oxygen. High catalytic activity was observed for all alkenes and this is the rst
instance of MOF epoxidation using molecular oxygen, a ubiquitous industrial oxidant.
Another MOF containing the same catalytically active porphyrin but in a
dierent topology, MOF-545-Mn, was also tested for catalytic activity to determine
the eect of MOF topology on heterogeneous catalysis.
The variation of pore metrics is demonstrated through each chapter and show
how powerful and useful reticular chemistry is through variation of structural
elements for specic uses. While catalytic MOFs are in their infancy, the future is
bright for catalytically active MOFs to come to the forefront of chemical industry.
