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.

自组装现象允许结构通过利用局部力寻找最低能量配置，自行组织成规律图案。然而，由于理性界面两种不同材料的困难，在有序框架中组装有机和无机构建块仍是一项挑战。在本研究中，以多氧金属酸盐（POMs）和环糊精（CDs）作为分子构建块（MBBs）的集合物，产生了两种前所未有的POM-CD金属有机框架（MOFs），即[PW12O40]3–和α-CD MOF（POT-CD）以及[P10Pd15.5O50]19–和γ-CD MOF（POP-CD），它们具有与其单独的母体MBBs所不具备的独特性质。值得注意的是，POT-CD凭借其独特的“非晶化和粉化”过程，呈现出非传统的锂存储行为增强。这为具有调谐结构和定制功能的下一代混合材料开辟了新的途径。