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（Self-assembly）可通过局域作用力驱动结构自发形成规整排列，以达到最低能量构型。然而，由于难以实现两种异类材料的理性界面结合，在有序骨架中共组装有机与无机组装基元仍颇具挑战。本文以多金属氧酸盐（polyoxometalates, POMs）与环糊精（cyclodextrins, CDs）作为分子构筑基元（molecular building blocks, MBBs）进行组装，成功获得两种前所未有的多金属氧酸盐-环糊精-金属有机骨架（POM-CD-MOFs）材料，即由[PW₁₂O₄₀]³⁻与α-环糊精构筑的α-CD MOF（POT-CD），以及由[P₁₀Pd₁₅.₅O₅₀]¹⁹⁻与γ-环糊精构筑的γ-CD MOF（POP-CD）。二者均具备其孤立母体分子构筑基元所不具备的独特性能。尤为值得关注的是，POT-CD凭借独特的“非晶化与粉化”过程，展现出非传统的增强储锂行为。该研究为构建结构可调、功能定制的新一代杂化材料开辟了全新途径。