Cationic arene ruthenium metalla-prisms of the general formula [Ru6(p-cymene)6(3-tpt)2-(OO∩OO)3] (3-tpt = 2,4,6tris(3-pyridyl)-1,3,5-triazine; OO∩OO = 5,8-dioxido-1,4-naphthoqui-nonato [1]6þ or 6,11-dioxido-5,12naphthacenedionato [2]6þ) have been obtained from the corresponding dinuclear arene ruthenium complexes [Ru2(pcymene)2(OO∩OO)Cl2] by reaction with 3-tpt, silver trifluoromethanesulfonate...

The geometry of cationic silicon clusters doped with vanadium, Si(n)V(+) (n=12-16), is investigated by using infrared multiple photon dissociation of the corresponding rare gas complexes in combination with ab initio calculations. It is shown that the clusters are endohedral cages, and evidence is provided that Si(16)V(+) is a fluxional system with a symmetric Frank-Kasper geometry.

The cationic cages nido-[C2Bu(t)2P2E]+ (E = As, Sb), which are isolobal to the cyclopentadienyl cation, adopt square based pyramidal structures with the heavy pnictogen atom at the apex; NMR and computational methods have been used to probe the dynamic behaviour of the complexes.

The presence of specific hydrocarbon gas molecules in various types of water cavities in natural gas hydrates (NGHs) are governed by the relative stabilities of these encapsulated guest molecule-water cavity combinations. Using molecular quantum chemical dispersion-corrected hybrid density functional computations, the interaction (ΔE(host--guest)) and cohesive energies (ΔE(coh)), enthalpies, an...

Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf)(OTf)₂ (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both species are fully characterized and are constituted of 12 electro-active subunits that can be reversibly oxidi...

Many natural proteins self-assemble, either to fulfill their biological function or as part of a pathogenic process. Biological assembly phenomena such as amyloidogenesis, domain swapping and symmetric oligomerization are inspiring new strategies for designing proteins that self-assemble to form supramolecular complexes. Recent advances include the design of novel proteins that assemble into fi...

This paper reviews some of the more interesting and recent phenomena associated with the metal ion cage chemistry involving hexaazamacropolycycles. Synthetic aspects are addressed in relation to making cages with smaller and larger hole sizes in order to modulate redox potentials and electron transfer rates. The introduction of substituents is also examined in relation to these factors along wi...

This 'Perspective' article summarises recent work from the authors' research group on the exploitation of the simple fac/mer geometric isomerism of octahedral metal tris-chelates as a tool to control the chemistry of coordination cages based on bis(pyrazolyl-pyridine) ligands, in two different respects. Firstly this geometric isomerism plays a major role in controlling the guest binding propert...