1 research outputs found
Post-Synthetic Annealing: Linker Self-Exchange in UiO-66 and Its Effect on Polymer–Metal Organic Framework Interaction
Post-synthetic
exchange (PSE) and defect engineering have emerged
as powerful techniques for tuning the properties and introducing novel
functionality to metal organic frameworks (MOFs). Growing evidence
suggests that each technique plays a key role in the mechanism of
the other: linker coordination chemistry is pivotal to defective frameworks,
while defect sites can help initiate PSE. Here, the intersection of
these approaches is explored by exchanging an MOF with linkers already
present within the framework. Post-synthetic annealing (PSA) modifies
an MOF’s properties by redistributing the framework’s
mixture of bound linker/modulator species. Using changes to the polymer-additive
interactions in poly-1-trimethylsilyl-1-propyne nanocomposites observed
through aging, we demonstrate that PSA causes one linker species to
preferentially accumulate on the MOF’s crystal surface. Reaction
conditions are shown to affect molecular composition of the resulting
annealed UiO-66 MOFs, a finding explained through established reaction
constants. This work simultaneously reveals intricacies of post-synthetic
modification chemistry and presents a facile means of tuning MOFs
and MOF nanocomposites