Polyoxometalates (POMs) are discrete anionic metaloxygen clusters which can be regarded as soluble oxide fragments. They exhibit a great diversity of sizes, nuclearities, and shapes. They are built from the connection of {MOx} polyhedra, M being a d-block element in high oxidation state, usually VIV,V, MoVI, or WVI.1 While these species have been known for almost two centuries, they still attract much interest partly based on their large domains of applications. They play a great role in various areas ranging from catalysis,2 medicine,3 electrochemistry,4 photochromism,5 to magnetism.6 This palette of applications is intrinsically due to the combination of their added value properties (redox properties, large sizes, high negative charges, nucleophilicity...). Parallel to this domain, the organic-inorganic hybrids area has followed a similar expansion during the last 10 years. The concept of organic-inorganic hybrid materials * To whom correspondence should be addressed. E-mail: dolbecq@ chimie.uvsq.fr. Chem. Rev. 2010, 110, 6009–6048 6009

Hybrid Organic−Inorganic Polyoxometalate Compounds: From Structural Diversity to Applications

This review (over 380 references) summarizes metal–organic frameworks (MOFs), Materials Institute Lavoisier (MILs), iso-reticular metal–organic frameworks (IR-MOFs), porous coordination networks (PCNs), zeolitic metal–organic frameworks (ZMOFs) and porous coordination polymers (PCPs) with selected examples of their structures, concepts for linkers, syntheses, post-synthesis modifications, metal nanoparticle formations in MOFs, porosity and zeolitic behavior for applications in gas storage for hydrogen, carbon dioxide, methane and applications in conductivity, luminescence and catalysis.

MOFs, MILs and more: concepts, properties and applications for porous coordination networks (PCNs)

Triazoles and tetrazoles: Prime ligands to generate remarkable coordination materials

The articles published in the tenth anniversary issue of CrystEngComm are reviewed. The issue highlighted the state-of-the-art of crystal engineering and new trends and developing areas in crystal engineering. In particular, the following article emphasises developments in the areas of intermolecular interactions, notably hydrogen and halogen bonds; metal–organic frameworks or coordination polymers; polymorphism and solvates.

Recent advances in crystal engineering

Surfactant-Assisted Synthesis of Nanoscale Gadolinium Metal–Organic Frameworks for Potential Multimodal Imaging†

Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu6(btp)3(P2W18O62)]·3H2O (1) (btp = 1,3-bis(1,2,4-triazol-1-y1)propane), [Cu6(btb)3((P2W18O62)]·2H2O (2), [Cu3(btb)6(P2W18O62)]·6H2O (btb = 1,4-bis(1,2,4-triazol-1-y1)butane) (3), and [Cu3(btx)5.5((P2W18O62)]·4H2O (btx = 1,6-bis(1,2,4-triazol-1-y1)hexane) (4), were synthesized and structurally characterized. In compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P2W18O62]6− anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu−btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu−btb layers to construct a 3D structure. Compound 3 exhibits a (42·62·82) 3D Cu−btb framework with square and hexagonal channels arranged alternately. The hexa-dentate polyoxoanions incorporate only into the hexagonal channels. In compoun...

Assembly of the Highest Connectivity Wells-Dawson Polyoxometalate Coordination Polymer: the Use of Organic Ligand Flexibility

Using low-temperature hydrothermal methods, nanoscale lanthanide phenylphosphonates species with different morphologies, namely, nanoparticles and nanorods, have been systematically synthesized. The possible growth mechanism of these nanorods was discussed. X-ray diffraction, transmission electron microscopy, electron diffraction, and photoluminescence spectra were used to characterize these materials. The photoluminescent properties of Eu(O3PC6H5)(HO3PC6H5) and La0.91Eu0.09(O3PC6H5)(HO3PC6H5) nanorods were discussed.

Systematic synthesis and characterization of single-crystal lanthanide phenylphosphonate nanorods.

Target syntheses of saturated Keggin polyoxometalate-based extended solids

The controlled synthesis of Eu2(WO4)3 nanostructures with different morphologies, namely ellipsoidlike, rodlike, cubelike, rod-bundlelike, and mesoporous spindlike, has been successfully achieved by the cationic surfactant-CTAB (cetyltrimethylammoniumbromide)-microemulsion-mediated and anionic surfactant-SDS (sodium dodecyl sulfate)-microemulsion-mediated solvothermal method separately. Various comparison experiments showed that fundamental experimental parameters, such as the water content, reaction temperature and the type of surfactants played important roles in the morphological control of Eu2(WO4)3 nanostructures. The possible growth mechanisms of these nanocrystals were elucidated in detail.

Jian-Fang Ma

Papers

Assembly of the Highest Connectivity Wells-Dawson Polyoxometalate Coordination Polymer: the Use of Organic Ligand Flexibility

Systematic synthesis and characterization of single-crystal lanthanide phenylphosphonate nanorods.

Target syntheses of saturated Keggin polyoxometalate-based extended solids

Microemulsion-mediated solvothermal synthesis and photoluminescent properties of europium tungstate nanostructures.