We report here a facile synthetic and analytical approach that allows us to identify and characterize functionalized polyoxomolybdate clusters that form upon the partial reduction of Mo(VI) salts in the presence of organoarsonate ligands. We demonstrated that electrospray ionization mass spectrometry, in combination with X-ray crystallography, provides an extremely powerful tool, allowing us to exploit slight perturbations of the ligand structures for the preparation of a series of unprecedented cluster compounds. Redox-active transition metals that adopt cubane or related structures are of particular interest because of their resemblance to active sites of enzymes. Our investigations underline the stability of the hybrid compounds in solution, an essential requirement for potential applications as catalysts. Supplemental analyses include measurements of the magnetic properties, NMR, IR, UV/vis, and bond-valence-sum analyses. Our results highlight the possibility of exploring real-time growth reactions of polyoxometales that emerge in solution and transform to produce hybrid organic-inorganic polyoxometalate clusters.

Put a spin on it: a {Mn(13)} coordination cluster has been used as a secondary building unit for the preparation of an open-framework structure for which the magnetic properties can be modified by solution adsorption of tetracyanoquinodimethane radical anions (TCNQ·(-)). The applied supramolecular approach takes advantage of kinetically labile Jahn-Teller sites and can be generalised for the construction and post-synthetic modification of multifunctional materials.

We present herein a novel method to prepare free-standing Dried Foam Films (DFFs) whereby individual polynuclear manganese complexes cover quantitatively the holes of micro-grids; the fabricated, homogeneous films have a cross-sectional thickness of only ca. 5 nm and are characterised by high mechanical stability.

surface on a sub-monolayer scale giving rise to a 2D supramolecular structure that is comparable to the packing arrangements of the capsules in the crystal structures.The synthesis and characterisation of metallo-supramolecular cages and molecular capsules have received significant scientific attention. 1,2In the last few decades preparative efforts were directed towards the synthesis of new cage topologies or homologous species with controllable inner cavities whose chemical, geometrical and electronic attributes may give rise to unique properties that can be exploited in homogeneous catalytic processes, size-and shape-restrictive chemical transformations, separations, drug delivery and sensing devices. 2,3Importantly, for the majority of these and other advanced applications, the stability of the assembled molecular species in solution is a key requirement. (Fig. 1). We highlight the solution stability of this class of compounds and demonstrate that individual cluster entities can be deposited on the Au(111) surface and imaged using a scanning tunneling microscope (STM).Polyoxometalates constitute an interesting class of compounds for the preparation of cages. 6 The chemistry of polyoxovanadates in aqueous reaction systems as developed by Müller, Zubieta and others is characterised by condensation reactions whereby V IV and to a certain extent V V species in predominantly square pyramidal coordination environments aggregate to form oligonuclear and polynuclear clusters. The geometrical restraints associated with the square pyramidal {OQVO 4 } building unit often lead to convex oligonuclear species