Supramolecular Frameworks Based on Rhenium Clusters Using the Synthons Approach.

The reaction of the K[{ReS}(OH)]·8HO rhenium cluster salt with pyrazine (Pz) in aqueous solutions of alkaline or alkaline earth salts at 4 °C or at room temperature leads to apical ligand exchange and to the formation of five new compounds: [{ReS}(Pz)(OH)(HO)] (), [{ReS}(Pz)(OH)(HO)] (), (NO)[{ReS}(Pz)(OH)(HO)](Pz)·3HO (), [Mg(HO)][{ReS}(Pz)(OH)(HO)]·8.5HO (), and K[-{ReS}(Pz)(OH)(HO)]·8HO (). Their crystal structures are built up from - or -[{ReS}(Pz)(OH)(HO)] cluster units.

Unprecedented electron-poor octahedral Ta(6) clusters in a solid-state compound: synthesis, characterisations and theoretical investigations of Cs(2)BaTa(6)Br(15)O(3).

The crystal structure of Cs2BaTa6Br15O3 has been elucidated by using synchrotron X-ray powder diffraction and absorption experiments. It is built from edge-bridged octahedral [(Ta6Bri9Oi3)Bra6]4− cluster units with a singular poor metallic electron (ME) count equal to thirteen. This leads to a paramagnetic behaviour related to one unpaired electron.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone.

Computationally assisted identification of functional inorganic materials.

The design of complex inorganic materials is a challenge because of the diversity of their potential structures. We present a method for the computational identification of materials containing multiple atom types in multiple geometries by ranking candidate structures assembled from extended modules containing chemically realistic atomic environments. Many existing functional materials can be described in this way, and their properties are often determined by the chemistry and electronic structure of their constituent modules.

Tuning of water and hydroxide content of intercalated Ruddlesden-Popper-type oxides in the PrSr3Co1.5Fe1.5O(10-δ) system.

A series of hydration experiments of the Ruddlesden-Popper phase PrSr(3)Co(1.5)Fe(1.5)O(10-δ) with varying levels of oxygen nonstoichiometry were performed with the goal to clarify phase formation and underlying mechanisms and driving forces.