Polyoxometalate–Cyclodextrin Metal–Organic Frameworks: From Tunable Structure to Customized Storage Functionality

Self-assembly
allows structures to organize themselves into regular
patterns by using local forces to find the lowest-energy configuration.
However, assembling organic and inorganic building blocks in an ordered
framework remains challenging due to  difficulties in rationally
interfacing two dissimilar materials. Herein, the ensemble of polyoxometalates
(POMs) and cyclodextrins (CDs) as molecular building blocks (MBBs)
has yielded two unprecedented POM-CD-MOFs, namely [PW12O40]3– and α-CD MOF (POT-CD) as well as [P10Pd15.5O50]19– and γ-CD MOF (POP-CD), with distinct
properties not shared by their isolated parent MBBs. Markedly, the POT-CD features a nontraditional enhanced Li storage behavior
by virtue of a unique “amorphization and pulverization”
process. This opens the door to a new generation of hybrid materials
with tuned structures and customized functionalities.