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 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

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Photo- and Electrochromism of Polyoxometalates and Related Materials

[Mo154(NO)14O420(OH)28(H2O)70](25 ± 5)−: A Water‐Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000

Magneto‐Structural Correlations in Dinuclear d1d1 Complexes: Structure and Magnetochemistry of Two Ferromagnetically Coupled Vanadium(IV) Dimers

Co-registered molecular logic gates combine two different inputs and outputs, such as light and matter. We introduce a biocompatible CO-releasing molecule (CORM, A) as Mn(I) tricarbonyl complex with the ligand 5-(dimethylamino)-N, N-bis(pyridin-2-ylmethyl) naphthalene-1-sulfonamide (L). CO release is chaperoned by turn-on fluorescence and can be triggered by light (405 nm) as well as with hydrogen peroxide in aqueous phosphate buffer. Complex A behaves as a logic “OR” gate via co-registering the inputs of irradiation (light) and peroxide (matter) into the concomitant outputs fluorescence (light) and CO (matter). Cell viability assays confirm the low toxicity of A toward different human cell lines. The CORM has been used to track the inclusion of A into cancer cells.

Co-Registered Molecular Logic Gate with a CO-Releasing Molecule Triggered by Light and Peroxide

The Schiff-base ligand derived from salicylaldehyde and γ-hydroxybutanoic acid hydrazide (H2Salhyhb) reacts with potassium metavanadate and hydrogen peroxide in a water/methanol solution with a pH value of around two to yield the corresponding vanadium(V) oxoperoxo complex [VO(O2)HSalhyhb(H2O)] (1). Complex 1 crystallizes with one molecule of water as 1·H2O in the monoclinic space group P21/n. For the vanadium atom a pentagonal-bipyramidal coordination geometry is observed, with a side-on bonded peroxo ligand in the equatorial plane. The hydroxy side chain of the hydrazide ligand is involved in a hydrogen-bond network with the peroxo ligand at the vanadium atom. This network shows some similarities with the hydrogen-bonding scheme found for the peroxo form of vanadium haloperoxidases. The stoichiometric reaction of 1 with 1,3,5-trimethoxybenzene (TMB) in the presence of tetrabutylammonium bromide leads to the formation of 1-bromo-2,4,6-trimethoxybenzene (Br-TMB), thus mimicking the oxidative halogenation function of the native enzyme. Complex 1 is also capable of oxidizing triphenylphosphane and methylphenylsulfane, yielding a cis-dioxovanadium(V) complex and the corresponding phosphane or sulfane oxide, respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Vanadium(V) Oxoperoxo Complexes with Side Chain SubstitutedN‐Salicylidenehydrazides: Modeling Supramolecular Interactions inVanadium Haloperoxidases

http://www.kimyakongreleri.org/2011/2011-166.pdf

Synthesis, spectroscopic characterization and biological activity of the metal complexes of the Schiff base derived from phenylaminoacetohydrazide and dibenzoylmethane

Winfried Plass

Papers

[Mo154(NO)14O420(OH)28(H2O)70](25 ± 5)−: A Water‐Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000

Magneto‐Structural Correlations in Dinuclear d1d1 Complexes: Structure and Magnetochemistry of Two Ferromagnetically Coupled Vanadium(IV) Dimers

Co-Registered Molecular Logic Gate with a CO-Releasing Molecule Triggered by Light and Peroxide

Vanadium(V) Oxoperoxo Complexes with Side Chain SubstitutedN‐Salicylidenehydrazides: Modeling Supramolecular Interactions inVanadium Haloperoxidases

Synthesis, spectroscopic characterization and biological activity of the metal complexes of the Schiff base derived from phenylaminoacetohydrazide and dibenzoylmethane