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

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

Designed Synthesis of POM–Organic Frameworks from {Ni6PW9} Building Blocks under Hydrothermal Conditions

Self-assembly of nanometer-scale [Cu24I10L12]14+ cages and ball-shaped Keggin clusters into a (4,12)-connected 3D framework with photoluminescent and electrochemical properties.

Ce(NO3)3·6H2O or Pr(NO3)3·6H2O and pyridine-2,6-dicarboxylic acid form a linear coordination polymeric structure under hydrothermal conditions. Hexameric water clusters join these linear chains through bonding to the metal ions. Other coordinated water and the carboxylate oxygen form an intricate array of hydrogen bonding resulting in a 3D network where each metal ion shows 9-coordination with an approximate D3 symmetry. Dimeric water clusters are also located in the void spaces. In the structure containing Pr(III), the water dimers are hydrogen-bonded to the hexamers, whereas in the Ce(III) structure, the dimers and the hexamers are far apart.

Coexistence of water dimer and hexamer clusters in 3D metal-organic framework structures of Ce(III) and Pr(III) with pyridine-2,6-dicarboxylic acid.

The three-dimensional framework of [Gd(H2O)3]3[GdMo12O42]vdt·3H2O, which was synthesized from hydrothermal reaction, is built up from Silverton-type anions linked by nine coordinated gadolinium(III...

Hydrothermal Assembly of a Novel Three-Dimensional Framework Formed by [GdMo12O42]9- Anions and Nine Coordinated GdIII Cations

Three compounds, [Cu(4,4‘-bpy)]2MoO4·2H2O (1), [Cu(4,4‘-bpy)]2Mo2O7 (2), and [Cu(4,4‘-bpy)(nic)(H2O)]2Mo8O26 (3), are synthesized by hydrothermal reaction, which suggests that oxomolybdate−organic ligand coordination transition-metal fragments can merge their merit to generate some interesting architectures. Crystal data for [Cu(4,4‘-bpy)]2MoO4·2H2O (1):  monoclinic system, space group C2/c, a = 10.936(1), b = 17.775(1), and c = 14.484(1) A, β = 110.15(1)°, and Z = 4. Crystal data for [Cu(4,4‘-bpy)]2Mo2O7 (2):  orthorhombic system, space group Pbcn, a = 11.841(1), b = 9.105(1), and c = 21.311(1) A, and Z = 4. Crystal data for [Cu(4,4‘-bpy)(nic)(H2O)]2Mo8O26 (3):  monoclinic system, space group P2(1)/n, a = 11.457(1), b = 16.918(1), and c = 12.463(1) A, β = 92.6(1)°, and Z = 2. Compound 1 is built up from {MoO4} tetrahedra linking of 4,4‘-bpy coordination copper(I) chain fragments as a railroad-like framework. Compound 2 has noticeable structural features:  two {Mo2O7} and four {CuO2N2} tetrahedra are conn...

Jin-Shun Huang

Papers

Hydrothermal Assembly of a Novel Three-Dimensional Framework Formed by [GdMo12O42]9- Anions and Nine Coordinated GdIII Cations

Three Polymeric Frameworks Constructed from Discrete Molybdenum Oxide Anions and 4,4‘-bpy-Bridged Linear Polymeric Copper Cations

A novel left-handed double helicate constructed from L-tartrate bridged molybdenum(VI) and gadolinium(III) atoms

Hydrothermal Assembly of a Novel Three‐Dimensional Framework Formed by [GdMo12O42]9‐ Anions and Nine Coordinated GdIII Cations.