The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

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Engineering coordination polymers towards applications

Polyoxometalates represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form structures that can bridge several length scales. The new building block principles that have been discovered are beginning to allow the design of complex clusters with desired properties and structures and several structural types and novel physical properties are examined. In this critical review the synthetic and design approaches to the many polyoxometalate cluster types are presented encompassing all the sub-types of polyoxometalates including, isopolyoxometalates, heteropolyoxometalates, and reduced molybdenum blue systems. As well as the fundamental structure and bonding aspects, the final section is devoted to discussing these clusters in the context of contemporary and emerging interdisciplinary interests from areas as diverse as anti-viral agents, biological ion transport models, and materials science.

Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices

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

The literature on open-framework materials has shown numerous examples of porous solids with additional structural, chemical, or physical properties. These materials show promise for applications ranging from sensing, catalysis and separation to multifunctional materials. This critical review provides an up-to-date survey to this new generation of multifunctional open-framework solids. For this, a detailed revision of the different examples so far reported will be presented, classified into five different sections: magnetic, chiral, conducting, optical, and labile open-frameworks for sensing applications. (413 references.)

Old materials with new tricks: multifunctional open-framework materials.

Chiral 3D Architectures with Helical Channels Constructed from Polyoxometalate Clusters and Copper–Amino Acid Complexes

A New 5‐Aminoisophthalic Acid bridged Cobalt(II) Polymeric Complex obtained by Hydrothermal Reaction

A novel acetated 54-member crown-shapedpolyoxomolybdate with unprecedented structural features:Na26[{Na(H2O)2}6({μ3-OH)4MoV20MoVI34O164(μ2-CH3COO)4}]·≈120H2O

By chemically embellishing metal−oxygen fragments into the three outer cavities of the nanoanion [H3- Mo57V6(NO)6O183(H2O)18]21- ({Mo57V6}), a new nanostructural anion formulated as [H3Mo57V6(NO)6O189- (H2O)12(VO)6]15- ({Mo57V12}) was obtained. The embellishment leads to a new nanostructural anion with some interesting results. Furthermore, the six embedded symmetry-related V2 centers have tetrahedral coordination environments and are verified as VV ions via solid-state 51V NMR spectrum.

(NH4)15[H3Mo57V6(NO)6O189(H2O)12(VO)6].approximately60H2O: new nanocompound obtained by chemical embellishment of [M57V6].

Synthesis and crystal structure of a new samarium borosilicate compound Sm3BSi2O10

The reaction of an aqueous solution of sodium molybdate with iron powder at low pH (∼0184) gives rise to the formation of a six-member Mo ring-shape cluster with an Fe (II) encapsulated at the center, [Na4(H2O)7][Fe(OH)6Mo6O18](1), which is further linked to a remarkable three-dimensional network via sodium ions

Hong-Hui Zhuang

Papers

A New 5‐Aminoisophthalic Acid bridged Cobalt(II) Polymeric Complex obtained by Hydrothermal Reaction

A novel acetated 54-member crown-shapedpolyoxomolybdate with unprecedented structural features:Na26[{Na(H2O)2}6({μ3-OH)4MoV20MoVI34O164(μ2-CH3COO)4}]·≈120H2O

(NH4)15[H3Mo57V6(NO)6O189(H2O)12(VO)6].approximately60H2O: new nanocompound obtained by chemical embellishment of [M57V6].

Synthesis and crystal structure of a new samarium borosilicate compound Sm3BSi2O10

[Na4(H2O)7][Fe(OH)6Mo6O18]: A new [12] metallacrown-6 structure with an octahedrally coordinated iron at the center