多酸导向的间苯二酚杯[4]芳烃[Co_(8)]配位笼的组装及电化学性质

Polyoxometalate‑directing calix[4]resorcinarene‑based giant[Co_(8)]coordination cage:Self‑assembly and electrochemical performance

基于多金属氧酸盐(POM)的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM-杯芳烃的大型[Co_(8)]配位笼[Co_(8)(MTR4A)_(6)Cl_(8)](α-SiW_(12)O_(40))_(2)·30DMF·74EtOH(cage-1),该配位笼由6个碗状间苯二酚杯[4]芳烃(MTR4A)分子、8个Co(Ⅱ)阳离子、2个α-SiW_(12)O_(40)^(4-)抗衡阴离子和8个Cl-阴离子组装而成。值得注意的是,α-SiW_(12)O_(40)^(4-)阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage-1表现出良好的锂离子存储能力。cage-1也能够实现对亚硝酸盐(NO_(2)^(-))的还原和抗坏血酸(AA)的氧化,是一种具有高活性的双功能催化剂。

Polyoxometalate(POM)‑based supramolecular coordination cages have aroused wide interest in terms of their design and fabrication,however,it still be challenging.Herein,we report a POM‑calixarene‑based giant[Co_(8)]coordination cage,[Co_(8)(MTR4A)_(6)Cl_(8)](α-SiW_(12)O_(40))_(2)·30DMF·74EtOH(cage‑1),assembled with six bowl‑shaped calix[4]resorcinarene(MTR4A)molecules,eight Co􀃭cations,twoα‑SiW_(12)O_(40)^(4-)counter anions,and eight Cl-anions.Remarkably,α‑SiW_(12)O_(40)^(4-)anions were sandwiched between layers via hydrogen‑bonded to form a 3D supramolecular architecture.Moreover,cage‑1 showed a good lithium‑ion storage capacity as an anode material in lithium‑ion batteries(LIBs).Furthermore,it was shown to be a highly active bifunctional electrocatalytic performance for reducing nitrite(NO_(2)^(-))and oxidizing ascorbic acid(AA).CCDC:2248724.