The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K4 @{[Cu29 (OH)7 (H2 O)2 (en)8 (trz)21 ][Nb24 O67 (OH)2 (H2 O)3 ]4 } and [Cu(en)2 ]@{[Cu2 (en)2 (trz)2 ]6 (Nb68 O188 )} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic-organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage-based extended assembly to form a 3D cage framework {[Cu(en)2 ]@{[Cu2 (trz)2 (en)2 ]6 [H10 Nb68 O188 ]}}. These materials exhibit visible-light-driven photocatalytic H2 evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic-organic hybrid PONb chemistry.

Inorganic–Organic Hybrid Polyoxoniobates: Polyoxoniobate Metal Complex Cage and Cage Framework

A series of DyxEr(1–x)-polyoxometalates (POMs) were successfully synthesized and characterized well by various physicochemical analysis. The structurally isolated compounds exhibit three characteristic emissions at 480 nm (blue, 4F9/2 → 6H15/2 transition), 573 nm (yellow, 4F9/2 → 6H13/2 transition), and 663 nm (red, 4F9/2 → 6H11/2 transition) whose luminescent color coordinates appear in the near-white area in the CIE 1931 chromaticity diagram. Time-resolved emission spectroscopy was used in DyxEr(1–x)-POM to further authenticate energy transfer from the photoexcitation O → M ligand to the metal charge-transfer state of phosphotungstate components to active Dy3+/Er3+ ions and energy transfer between Dy3+ ion and Er3+ ion via intramolecular energy transitions. The relative emission intensity of ∼32%, ∼53%, and ∼85% for Dy-POM, Dy0.9Er0.1-POM, and Dy0.8Er0.2-POM respectively, were obtained under 300 min of UV irradiation, which indicates better photostability of Dy0.8Er0.2-POM. Furthermore, DyxEr(1–x)-POM s...

Enhanced Photostability Luminescent Properties of Er3+-Doped Near-White-Emitting DyxEr(1–x)-POM Derivatives

Two unprecedented examples of cluster organic frameworks (TBA)3Cu[V6O13(L)2]2·4DEF (2) (TBA)Ag[V6O13(L)2] solvent (3) (TBA = tetrabutylammonium, H3L = tris(hydroxymethyl)-4-picoline, DEF = N, N'-diethylformamide) based on Lindqvist-type polyoxometalate (POM) secondary building units (SBUs) have been constructed successfully. Compounds 2 and 3 are the second cases of cluster organic frameworks based on Lindqvist-type POM cluster SBUs. Furthermore, the cluster organic framework of 2 exhibits efficient electrocatalytic activity and strong durability in oxygen reduction reaction.

Designed Construction of Cluster Organic Frameworks from Lindqvist-type Polyoxovanadate Cluster.

Four new hybrid architectures containing a [Co2Mo10H4O38]6– polyoxoanion, (en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O (1), (Hbim)2[{Cu(bim)2(H2O)2}2{Co2Mo10H4O38}]·5H2O (2), H2[Cu(dpdo)3(H2O)4][{Cu2(dpdo)3(H2O)4(CH3CN)}2{Co2Mo10H4O38}2]·9H2O (3), and (H2bpp)4[{Cu(H2O)2}{NaCo2Mo10H4O38}2]·10H2O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4′-bipyridine-N,N′-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host–guest framework composed of 3D Cu-ptz as the host and Evans–Showell-type polyoxoanion [Co2Mo10H4O38]6– as the guest. Compound 2 is constructed from [Co2Mo10H4O38]6– polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [Co2Mo10H4O38]6– polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is...

Evans–Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic–Organic Hybrid Compounds with Copper–Organic Coordination Complexes: Synthesis and Oxidation Catalysis

Polyoxometalates: Tailoring metal oxides in molecular dimension toward energy applications

A luminescent polyoxoniobate lanthanide derivative {Eu3(H2O)9[Nb48O138(H2O)6]}27- .

A highly efficient Rh(III)-catalyzed cascade C-H activation/annulation of sulfoximines with iodonium ylides under metal-oxidant-free conditions has been reported. The fused cyclohexanone-1,2-benzothiazine scaffold is readily achieved with a one-pot process in this reaction. This protocol exhibits good functional group tolerance and moderate to excellent yields. Additionally, the olefination of the target product illustrates the promising usefulness of this strategy.

Rhodium(III)-catalyzed cascade C-H functionalization/annulation of sulfoximines with iodonium ylides for the synthesis of cyclohexanone-1,2-benzothiazines.

Metal-Free Boron-Mediated ortho-C-H Hydroxylation of N-Benzyl-3,4,5-tribromopyrazoles.

A novel organic-inorganic hybrid polyoxometalate-based 3D framework constructed by organo-functionalized [As 2 W 21 O 72 (mal) 2 ] 18 − units and Ce 3 + ions

Yangyang Wang

Papers

A luminescent polyoxoniobate lanthanide derivative {Eu3(H2O)9[Nb48O138(H2O)6]}27- .

Rhodium(III)-catalyzed cascade C-H functionalization/annulation of sulfoximines with iodonium ylides for the synthesis of cyclohexanone-1,2-benzothiazines.

Metal-Free Boron-Mediated ortho-C-H Hydroxylation of N-Benzyl-3,4,5-tribromopyrazoles.

A novel organic-inorganic hybrid polyoxometalate-based 3D framework constructed by organo-functionalized [As 2 W 21 O 72 (mal) 2 ] 18 − units and Ce 3 + ions

Ligand-Enabled Sequential C(sp3)-H and C(sp2)-H Diolefination Reaction via Palladium Catalyst.