Search

• Three supramolecular structures are obtained by anchoring POMs to POMOFs. • These supramolecular showcase diverse Li+ storage and transmission channels. • The semi-encapsulated channel demonstrating remarkable electrochemical performance. • The supramolecular architecture facilitates the uniform dispersion of POMs. • POMOFs present active N and S sites, enhancing the adsorption for Li+. Polyoxometalates (POMs) have attracted considerable attention in research due to their efficient multi-electron collection and distribution capabilities. Overcoming the challenges associated with their practical application as anodes in Lithium-ion Batteries (LIBs) involves not only preventing POM dissolution in the electrolyte from the anode but also effectively utilizing their multi-electron storage and conversion properties. Three unique supramolecular frameworks have been successfully designed and synthesized, featuring customized channels optimized for LIBs. Particularly, the semi-encapsulated supramolecular structures, which demonstrate exceptional charge/discharge cycling performance and cycling rate capabilities compared to other configurations. Three distinct supramolecular frameworks have been successfully designed and synthesized, each featuring a tailored array of channels specifically optimized for Lithium-ion Batteries (LIBs). Of particular significance is the incorporation of "electron sponge" Polyoxometalates (POMs) within these structures, showcasing a diverse array of electrochemical properties influenced by structural nuances. These include the formation of electron bridges with metals and interactions with the sulfur active sites present in organic ligands. [Display omitted] [ABSTRACT FROM AUTHOR]

The first mixed-valence nickel-supported polyoxometalate-based metal–organic framework, (H2mim)[NiIII(Hmim)4][SiW11NiIIO37(OH)2(Hmim)]·3H2O (1) (Hmim = 2-methylimidazole), has been synthesized using a steam-assisted conversion method, and is constructed from noncovalent interactions (hydrogen bonds and π…π stacking interactions). 1 has a repeating honeycomb-shaped internal structure with one-dimensional channels along the direction of the c axis, where the diameter of the aperture is as large as 18.83 Å. Furthermore, the stability and the optical band gaps are investigated. [ABSTRACT FROM AUTHOR]

Self-assemblyof multiple components into well-defined and predictablestructures remains one of the foremost challenges in chemistry. Here,upon subtle ligand variation, we reported on the assembly of threenew polyoxometalate-based organic–inorganic hybrid compoundswith different helical channel, [Ag3(H2pyttz-I)2][PMo12O40] (1), [Ag6(H2pyttz-II)4][CoW12O40]·2H2O (2), and [Ag7(Hpyttz-II)3(H2pyttz-II)][GeW12O40]·7H2O (3) (H2pyttz-I/II= 4-/3-pyrid-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl,POM = polyoxometalates). X-ray diffraction analysis shows that compound 1is constructed by “butterfly-like” Ag5(H2pyttz-I)2subunits and POMs clusters,which are assembled into close helical channels impregnated with thecomponents selves. Both compounds 2and 3are constructed by “paddle-wheel like” Ag4(H2pyttz-II)4motifs and POMs clusters, whichbring into being the larger helical channels (10.5% and 12.5% of thecell volume, respectively). Note that the only difference in compounds 2and 3is that the former contains 1D metal–organicchain structure, and the latter contains 2D metal–organic layerstructure. In addition, the photocatalytic degradation of RhB by thesecompounds was also investigated. [ABSTRACT FROM AUTHOR]

To investigate the influence of reactive conditions onthe structures of Keggin POM supporting metal–organic frameworks(MOFs), five new compounds, [Ag6(2-pytz)4(H2O)2][HPMo12O40] (1), {[Ag14(2-pytz)12(H2O)4][H4PMo12O40]2}·2H2O (2), {[Ag6(2-pytz)4(H2O)4][H2SiW12O40)]}·6H2O (3), {[Ag3(3-pytz)2]2·[AgPMo12O40]}·2H2O (4), [Ag6(4-pytz)4][HPMo12O40] (5) [pytz = 5-(pyridyl)tetrazolate],were hydrothermally synthesized by tuning the reactive species andpH values and characterized by routine method and single-crystal X-raycrystallography. Although compounds 1–5all show the POM supporting 3D MOFs skeleton, MOFs exhibit diversestructures and POMs play different supporting functions, more specifically,pseudo POM chains supporting MOFs in 1and 2, isolated POM spheres supporting MOFs in 3, ture POMchains supporting MOFs in 4, and pseudo POM layers supportingMOFs in 5. The roles of the pH value, pytz derivatives,and the Keggin homologues in the formation of the POM supporting MOFshave been discussed. In addition, the photoluminescence propertiesof compounds 1–3were investigatedin the solid state at room temperature. [ABSTRACT FROM AUTHOR]