Polyoxometalates (POMs) are a subset of metal oxides that represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form dynamic structures that can range in size from the nano- to the micrometer scale Herein we present the very latest developments from synthesis to structure and function of POMs We discuss the possibilities of creating highly sophisticated functional hierarchical systems with multiple, interdependent, functionalities along with a critical analysis that allows the non-specialist to learn the salient features We propose and present a "periodic table of polyoxometalate building blocks" We also highlight some of the current issues and challenges that need to be addressed to work towards the design of functional systems based upon POM building blocks and look ahead to possible emerging application areas

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

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

Polyoxometalates (POMs) are a subset of metal oxides with unique physical and chemical properties, which can be reliably modified through various techniques and methods to develop sophisticated materials and devices. In parallel with the large number of new crystal structures reported in the literature, the application of these POMs towards multifunctional materials has attracted considerable attention. This critical review summarizes recent progress on POM-based molecular and composite materials, and particularly highlights the emerging areas that are closely related to surface, electronic, energy, environment, life science, etc. (171 references).

Recent advances on polyoxometalate-based molecular and composite materials

Die Polyoxometallate (POM), eine Untergruppe der Metalloxide, bilden vielfaltige Molekulcluster, die nicht nur auserordentlich vielfaltige physikalische Eigenschaften zeigen, sondern auch dynamische Strukturen mit Abmessungen vom Nanometer- bis zum Mikrometermasstab bilden konnen. Hier beschreiben wir die neuesten Entwicklungen von der Synthese bis zur Struktur und Funktion von Polyoxometallaten. Wir diskutieren Wege zur Herstellung hochst differenzierter hierarchischer Systeme mit mehreren voneinander unabhangigen Funktionalitaten und geben eine kritische Analyse, aus der auch nichtspezialisierte Leser die wichtigsten Eigenschaften ersehen konnen. In diesem Zusammenhang schlagen wir auch ein “Periodensystem der Polyoxometallat-Baueinheiten” vor. Schlieslich beleuchten wir einige aktuelle Herausforderungen beim Design funktioneller Systeme auf der Basis von POM-Baueinheiten und geben einen Ausblick auf mogliche Anwendungen.

Polyoxometallate als Bausteine für funktionelle Nanosysteme

The use of polyoxometalates in protein crystallography - An attempt to widen a well-known bottleneck.

The molecular recognition of polyoxometalates by human serum albumin is studied using two different polyoxometalates (POMs) at pH 7.5. The results are compared with those obtained at pH 3.5 and 9.0. At pH 7.5, both POMs strongly interact with the protein with different binding behaviors. The Keggin shaped POM, [H2W12O40]6- (H2W12), specifically binds the protein, forming a complex with a 1:1 stoichiometry with Ka = 2.9 × 106 M-1. The binding constant decreased dramatically with the increase of the ionic strength, thus indicating a mostly electrostatic binding process. Isothermal titration calorimetry (ITC) experiments show that the binding is an enthalpically driven exothermic process. For the wheel shaped POM [NaP5W30O110]14- (P5W30), there are up to five binding sites on the protein. Increasing the ionic strength changes the binding behavior significantly, leading to a simple exothermic process, with several binding sites. Competitive binding experiments indicate that the two POMs share one common bindi...

and Pedro de Oliveira

Papers

Polyoxometalate binding to human serum albumin: a thermodynamic and spectroscopic approach.