Stepwise assembly of an adamantoid Ru4Ag6 cage by control of metal coordination geometry at specific sites

The geometrically pure ‘complex ligand’ fac-[Ru(Lph)3]2+, in which three pendant bidentate binding sites are located on one face of the complex, reacts with Ag(I) ions to form the adamantoid decanuclear cage [{Ru(Lph)3}4Ag6](PF6)14 which contains a 6-coordinate Ru(II) ion at each vertex of a large tetrahedron and a 4-coordinate Ag(I) ion along each edge

Calculating the energy spectra of magnetic molecules: application of real- and spin-space symmetries

The determination of the energy spectra of small spin systems as for instance given by magnetic molecules is a demanding numerical problem. In this work we review numerical approaches to diagonalize the Heisenberg Hamiltonian that employ symmetries; in particular we focus on the spin-rotational symmetry SU(2) in combination with point-group symmetries. With these methods one is able to block-diagonalize the Hamiltonian and thus to treat spin systems of unprecedented size. In addition it provides a spectroscopic labeling by irreducible representations that is helpful when interpreting transitions induced by Electron Paramagnetic Resonance (EPR), Nuclear Magnetic Resonance (NMR) or Inelastic Neutron Scattering (INS). It is our aim to provide the reader with detailed knowledge on how to set up such a diagonalization scheme.Comment: 29 pages, many figure

Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage.

The hollow cavities of coordination cages can provide an environment for enzyme-like catalytic reactions of small-molecule guests. Here, we report a new example (catalysis of the Kemp elimination reaction of benzisoxazole with hydroxide to form 2-cyanophenolate) in the cavity of a water-soluble M8L12 coordination cage, with two features of particular interest. First, the rate enhancement is among the largest observed to date: at pD 8.5, the value of kcat/kuncat is 2 × 10(5), due to the accumulation of a high concentration of partially desolvated hydroxide ions around the bound guest arising from ion-pairing with the 16+ cage. Second, the catalysis is based on two orthogonal interactions: (1) hydrophobic binding of benzisoxazole in the cavity and (2) polar binding of hydroxide ions to sites on the cage surface, both of which were established by competition experiments

Photoinduced energy- and electron-transfer from a photoactive coordination cage to bound guests.

In a coordination cage which contains an array of twelve naphthyl chromophores surrounding a central cavity, photoinduced energy or electron-transfer can occur from the chromophore array to the bound guest in supramolecular host/guest complexes

Fac and mer isomers of Ru(II) tris(pyrazolyl-pyridine) complexes as models for the vertices of coordination cages: structural characterisation and hydrogen-bonding characteristics

We have prepared a series of mononuclear fac and mer isomers of Ru(II) complexes containing chelating pyrazolyl-pyridine ligands, to examine their differing ability to act as hydrogen-bond donors in MeCN. This was prompted by our earlier observation that octanuclear cube-like coordination cages that contain these types of metal vertex can bind guests such as isoquinoline-N-oxide (K = 2100 M−1 in MeCN), with a significant contribution to binding being a hydrogen-bonding interaction between the electron-rich atom of the guest and a hydrogen-bond donor site on the internal surface of the cage formed by a convergent set of CH2 protons close to a 2+ metal centre. Starting with [Ru(LH)3]2+ [LH = 3-(2-pyridyl)-1H-pyrazole] the geometric isomers were separated by virtue of the fact that the fac isomer forms a Cu(I) adduct which the mer isomer does not. Alkylation of the pyrazolyl NH group with methyl iodide or benzyl bromide afforded [Ru(LMe)3]2+ and [Ru(Lbz)3]2+ respectively, each as their fac and mer isomers; all were structurally characterised. In the fac isomers the convergent group of pendant –CH2R or –CH3 protons defines a hydrogen-bond donor pocket; in the mer isomer these protons do not converge and any hydrogen-bonding involving these protons is expected to be weaker. For both [Ru(LMe)3]2+ and [Ru(Lbz)3]2+, NMR titrations with isoquinoline-N-oxide in MeCN revealed weak 1 : 1 binding (K ≈ 1 M−1) between the guest and the fac isomer of the complex that was absent with the mer isomer, confirming a difference in the hydrogen-bond donor capabilities of these complexes associated with their differing geometries. The weak binding compared to the cage however occurs because of competition from the anions, which are free to form ion-pairs with the mononuclear complex cations in a way that does not happen in the cage complexes. We conclude that (i) the presence of fac tris-chelate sites in the cage to act as hydrogen-bond donors, and (ii) exclusion of counter-ions from the central cavity leaving these hydrogen-bonding sites free to interact with guests, are both important design criteria for future coordination cage hosts

Mapping the internal recognition surface of an octanuclear coordination cage using guest libraries

Size and shape criteria for guest binding inside the cavity of an octanuclear cubic coordination cage in water have been established using a new fluorescence displacement assay to quantify guest binding. For aliphatic cyclic ketones of increasing size (from C5 to C11), there is a linear relationship between ΔG for guest binding and the guest’s surface area: the change in ΔG for binding is 0.3 kJ mol–1 Å–2, corresponding to 5 kJ mol–1 for each additional CH2 group in the guest, in good agreement with expectations based on hydrophobic desolvation. The highest association constant is K = 1.2 × 106 M–1 for cycloundecanone, whose volume is approximately 50% of the cavity volume; for larger C12 and C13 cyclic ketones, the association constant progressively decreases as the guests become too large. For a series of C10 aliphatic ketones differing in shape but not size, ΔG for guest binding showed no correlation with surface area. These guests are close to the volume limit of the cavity (cf. Rebek’s 55% rule), so the association constant is sensitive to shape complementarity, with small changes in guest structure resulting in large changes in binding affinity. The most flexible members of this series (linear aliphatic ketones) did not bind, whereas the more preorganized cyclic ketones all have association constants of 104–105 M–1. A crystal structure of the cage·cycloundecanone complex shows that the guest carbonyl oxygen is directed into a binding pocket defined by a convergent set of CH groups, which act as weak hydrogen-bond donors, and also shows close contacts between the exterior surface of the disc-shaped guest and the interior surface of the pseudospherical cage cavity despite the slight mismatch in shape

Binding of chemical warfare agent simulants as guests in a coordination cage: contributions to binding and a fluorescence-based response.

Cubic coordination cages act as competent hosts for several alkyl phosphonates used as chemical warfare agent simulants; a range of cage/guest structures have been determined, contributions to guest binding analysed, and a fluorescent response to guest binding demonstrated

Stepwise synthesis of a Ru4Cd4 coordination cage using inert and labile subcomponents: introduction of redox activity at specific sites.

The kinetically inert mononuclear complex [RuL3](PF6)2 (1 : 3 mixture of fac and mer isomers), with three pendant binding sites, reacts with labile Cd(ii) ions to complete the assembly of a Ru4Cd4 cubic coordination cage in which reversible redox behaviour has been introduced at the Ru(ii) sites

Seeing and believing: Observing desistance-focused practice and enduring values in the National Probation Service

This article focuses on the feasibility of using a desistance-focused approach in the National Probation Service (NPS) in the post-Transforming Rehabilitation (TR) context. Findings are drawn from an exploratory study undertaken in one NPS Division, which used triangulation of three data collection methods; observations of one-to-one supervision sessions, documentary analysis and practitioner focus groups. Findings show that practitioners use elements of a desistance-focussed approach, although not exclusively. Values based upon belief in the capacity to change and the need to offer support endure, despite mass organisational upheaval. The article concludes by suggesting that this 'enduring habitus' of probation could be an enabler for a desistance-focused approach but instrumentalism in policy and practice is a significant barrier

Stimuli-Responsive Reversible Assembly of 2D and 3D Metallosupramolecular Architectures

The discovery of interconvertible platinum coordination modes, which reveals and masks cis coordinating groups upon addition of acid and base, respectively, has been exploited to facilitate stimuli-responsive assembly and disassembly of both two- and three-dimensional metallosupramolecular architectures. Treatment of a binclear platinum complex with acid along with ditopic and tritopic donor ligands generated a molecular square and a trigonal prism, respectively, in good to high yield. These complexes were unambiguously identified using electrospray mass spectrometry, H-1 NMR spectroscopy, and X-ray crystallography. Both assemblies can be disassembled into their constituent parts simply by treatment with base, and the prism can be cycled between the assembled and disassembled states by the alternate addition of acid and base.</p