Four 2D “Fully Reduced” Polyoxovanadates: Vanadium Oxide Clusters Encapsulating Different Guest Molecules

Four two-dimensional fully reduced polyoxovanadates, namely, [Cd­(DAP)₂]₄­[HV^III₃V^IV₁₈P₆O₆₀(DAP)₃­(HOCH₂CH₂OH)]·10H₂O <b>(1)</b>, [Cd­(DAP)₂]₄­[HV^III₃V^IV₁₈P₆O₆₀(DAP)₃­(CH₃OH)]·11H₂O <b>(2),</b> [Cd­(DAP)₂]₄­[HV^III₃V^IV₁₈P₆O₆₀(DAP)₃­(CH₃CH₂OH)]·4H₂O (<b>3</b>) and Co^III(DAP)₃­[Co^II(DAP)₂]₃[V^III₃V^IV₁₈P₆O₆₀(DAP)₃­(HOCH₂CH₂OH)]·14H₂O (<b>4</b>) were synthesized by virtue of the reducing power of alkylamine in hydrothermal conditions. Single-crystal X-ray structural analysis, magnetic measurement, IR spectroscopy, elemental analysis, and thermogravimetric measurements were performed to analyze the structures and properties of these four compounds. Structural analysis indicates that the four compounds contain the same huge low-valent vanadium oxide anion cages [V^III₃V^IV₁₈P₆O₆₀(DAP)₃]^9–, and the cages can catch different guest molecules. Four cages are linked by Co or Cd atoms to form a four-membered ring, while adjacent four-membered rings are connected to each other by sharing edges to make an inorganic–organic hybrid layer. The magnetic susceptibility measurements of four compounds indicate ferrimagnetic interactions between vanadium ions

Four 2D “Fully Reduced” Polyoxovanadates: Vanadium Oxide Clusters Encapsulating Different Guest Molecules

Four two-dimensional fully reduced polyoxovanadates, namely, [Cd­(DAP)₂]₄­[HV^III₃V^IV₁₈P₆O₆₀(DAP)₃­(HOCH₂CH₂OH)]·10H₂O <b>(1)</b>, [Cd­(DAP)₂]₄­[HV^III₃V^IV₁₈P₆O₆₀(DAP)₃­(CH₃OH)]·11H₂O <b>(2),</b> [Cd­(DAP)₂]₄­[HV^III₃V^IV₁₈P₆O₆₀(DAP)₃­(CH₃CH₂OH)]·4H₂O (<b>3</b>) and Co^III(DAP)₃­[Co^II(DAP)₂]₃[V^III₃V^IV₁₈P₆O₆₀(DAP)₃­(HOCH₂CH₂OH)]·14H₂O (<b>4</b>) were synthesized by virtue of the reducing power of alkylamine in hydrothermal conditions. Single-crystal X-ray structural analysis, magnetic measurement, IR spectroscopy, elemental analysis, and thermogravimetric measurements were performed to analyze the structures and properties of these four compounds. Structural analysis indicates that the four compounds contain the same huge low-valent vanadium oxide anion cages [V^III₃V^IV₁₈P₆O₆₀(DAP)₃]^9–, and the cages can catch different guest molecules. Four cages are linked by Co or Cd atoms to form a four-membered ring, while adjacent four-membered rings are connected to each other by sharing edges to make an inorganic–organic hybrid layer. The magnetic susceptibility measurements of four compounds indicate ferrimagnetic interactions between vanadium ions

An Unprecedented M–O Cluster Constructed from Nanosized {[C₅NH₅]₉[H₃₁Mo^V₁₂O₂₄Co^II₁₂(PO₄)₂₃(H₂O)₄]}^2– Anions Exhibiting Interesting Nonlinear-Optical Properties

A novel high-nuclear nanosized cluster modified by conjugated organic ligands (pyridine and imidazole), [C₅NH₅]₈­[C₃H₅N₂]₂­{[C₅NH₅]₉​­[H₃₁Mo₁₂O₂₄Co₁₂​­(PO₄)₂₃­(H₂O)₄]}·12H₂O (<b>1</b>), has been successfully isolated under hydrothermal conditions and structurally characterized. Compound <b>1</b> consists of 12 Co^II and 12 Mo^V ions linked by 23 {PO₄} groups, exhibiting unprecedented nanosized ship-shaped clusters. The magnetic measurements reveal that compound <b>1</b> exhibits dominant antiferromagnetic interactions. Additionally, pyridine and imidazole ligands enhance the delocalized electron effects of clusters, and the third-order nonlinear-optical response of compound <b>1</b> is excellent

POM Constructed from Super-Sodalite Cage with Extra-Large 24-Membered Channels: Effective Sorbent for Uranium Adsorption

A POMs-based sorbent functionalized by phosphate groups: H₃₃Na₁₄Mo^V₂₄Mo^VI₂(PO₄)₁₁O₇₃ has been successfully isolated under hydrothermal conditions. The cooperative assembly of the ring-shaped polyoxometalate structural building unit {P₄Mo₆} and MoO₄ tetrahedra linkers gives rise to an unprecedented supersodalite cage containing approximately spherical cavities with a 8.76 Å diameter. As POMs-based inorganic material, compound <b>1</b> was first applied as sorbent to adsorb U­(VI) from aqueous solution, exhibiting good stability, high efficiency, and selectivity. The maximum sorption capacity reaches 325.9 mg g^–1, which may capture radionuclides through cooperative binding of the phosphate groups. The adsorbed U­(VI) could be nearly drastically eluted when using 0.1 M Na₂CO₃ and the sorption capacity for U­(VI) slightly decreased 10.16% through five successive sorption/desorption cycles. This work represents first application of POMs-based inorganic materials as sorbent to adsorb uranium from aqueous solution and provides a feasible approach for the entrapment and recovery of radionuclides

A Novel Dumbbell-like Polyoxometalate Assembled of Copper(II)-Disubstituted Monovacant Keggin Polyoxoanions with a Tetranuclear Copper Cluster

A dimeric Keggin polyoxometalate, [Cu­(bpy)­(μ₂-OH)]₄[(H₂O)­(bpy)₂HPW₁₁Cu₂O₃₉]₂·2CH₃CH₂OH·10H₂O (<b>1</b>), constructed from two dicopper­(II)-substituted monovacant Keggin polyoxoanions bridged by a Cu₄ cluster, has been hydrothermally synthesized. Magnetic analysis indicates predominantly an antiferromagnetic interaction between copper­(II) centers. Compound <b>1</b> also shows very high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester

POM Constructed from Super-Sodalite Cage with Extra-Large 24-Membered Channels: Effective Sorbent for Uranium Adsorption

A POMs-based sorbent functionalized by phosphate groups: H₃₃Na₁₄Mo^V₂₄Mo^VI₂(PO₄)₁₁O₇₃ has been successfully isolated under hydrothermal conditions. The cooperative assembly of the ring-shaped polyoxometalate structural building unit {P₄Mo₆} and MoO₄ tetrahedra linkers gives rise to an unprecedented supersodalite cage containing approximately spherical cavities with a 8.76 Å diameter. As POMs-based inorganic material, compound <b>1</b> was first applied as sorbent to adsorb U­(VI) from aqueous solution, exhibiting good stability, high efficiency, and selectivity. The maximum sorption capacity reaches 325.9 mg g^–1, which may capture radionuclides through cooperative binding of the phosphate groups. The adsorbed U­(VI) could be nearly drastically eluted when using 0.1 M Na₂CO₃ and the sorption capacity for U­(VI) slightly decreased 10.16% through five successive sorption/desorption cycles. This work represents first application of POMs-based inorganic materials as sorbent to adsorb uranium from aqueous solution and provides a feasible approach for the entrapment and recovery of radionuclides