Nitroxide-nitroxide and nitroxide-metal distance measurements in transition metal complexes with two or three paramagnetic centres give access to thermodynamic and kinetic stabilities.

Fundamentally, the stability of coordination complexes and of templated (bio)macromolecular assemblies depends on the thermodynamic and kinetic properties of the intermediates and final complexes formed. Here, we used pulse EPR (electron paramagnetic resonance) spectroscopy to determine the stabilities of nanoscopic assemblies formed between one or two nitroxide spin-labelled tridentate 2,2':6',2''-terpyridine (tpy) ligands and divalent metal ions (FeII, ZnII, CoII and CuII). In three distinct approaches we exploited (a) the modulation depth of pulsed electron-electron double resonance (PELDOR) experiments in samples with increasing metal-to-ligand ratios, (b) the frequencies of PELDOR under broadband excitation using shaped pulses and (c) the distances recovered from well-resolved PELDOR data in fully deuterated solvents measured at 34 GHz. The results demonstrate that PELDOR is highly sensitive to resolving the stability of templated dimers and allows to readily distinguish anti-cooperative binding (for CuII ions) from cooperative binding (for CoII or FeII ions). In the case of paramagnetic ions (CoII and CuII) the use of broadband PELDOR allowed to identify the cooperativity of binding from the time domain and distance data. By using a second labelled tpy ligand and by mixing two homoleptic complexes of the same metal centre we could probe the kinetic stability on a timescale of tens of seconds. Here, tpy complexes of CuII and ZnII were found to be substitutionally labile, CoII showed very slow exchange and FeII was inert under our conditions. Not only do our chemical models allow studying metal-ligand interactions via PELDOR spectroscopy, the design of our study is directly transferable to (bio)macromolecular systems for determining the kinetic and thermodynamic stabilities underpinning (templated) multimerisation. Considering the limited methods available to obtain direct information on the composition and stability of complex assemblies we believe our approach to be a valuable addition to the armoury of methods currently used to study these systems.

Synthesis and characterization of photoluminescent vinylbiphenyl decorated polyhedral oligomeric silsesquioxanes.

Grubbs cross-metathesis has been used to functionalize octavinylsilsesquioxane with fluorescent vinylbiphenyl-modified chromophores to design new hybrid organic-inorganic nanomaterials. Those macromolecules have been characterized by NMR, microanalyses, MALDI-TOF mass spectrometry and photoluminescence. This last method was shown to be an interesting tool in the analysis of the purity of the cube derivatives.

Assessing dimerisation degree and cooperativity in a biomimetic small-molecule model by pulsed EPR.

Pulsed electron paramagnetic resonance (EPR) spectroscopy is gaining increasing importance as a complementary biophysical technique in structural biology. Here, we describe the synthesis, optimisation, and EPR titration studies of a spin-labelled terpyridine Zn(II) complex serving as a small-molecule model system for tuneable dimerisation.

Correction: Assessing dimerisation degree and cooperativity in a biomimetic small-molecule model by pulsed EPR.

Correction for 'Assessing dimerisation degree and cooperativity in a biomimetic small-molecule model by pulsed EPR' by K. Ackermann et al., Chem. Commun., 2015, 51, 5257-5260.

Aziridinyl anions from a chiral, nonracemic 2-isopropylidineaziridine: surprisingly diastereoselective alkylation reactions.

Lithiation and alkylation of a 2-isopropylidineaziridine bearing an (S)-alpha-methylbenzyl group on nitrogen proceeds with high levels of diastereocontrol (80-90% de).

pH dependent separation of uranium by chelation chromatography using pyridine 2,6-dimethanol as a chelator: single crystal X-ray structural confirmation of the chelated uranium complex.

A very effective sorbent material which exhibits exceptional capture of hexavalent uranium from other actinides and lanthanides at microg g(-1) level, features pyridine 2,6-dimethanol immobilized onto alumina. The maximum sorption capacity for dioxouranium(VI) was found as 1.96 mmol g(-1) at pH 3.0. The adsorbed uranium complex was eluted completely by 0.05 mol L(-1) (NH(4))(2)CO(3) solution and the concentration of hexavalent dioxouranium ion was monitored spectrophotometrically using Arsenazo III. The structure of the chelated uranium complex has been confirmed by single crystal X-ray structure analysis and Fourier transform infrared red (FTIR) spectroscopy. Thermo gravimetric analysis/differential thermo gravimetric analysis (TGA/DTG) of the chelated uranium complex was performed. The method is reproducible with a relative standard deviation (RSD) of 1.2% (N=10) and the three sigma detection limits (N=15) 1.2 microg mL(-1) respectively. A pre-concentration factor, almost 500, for uranium was achieved. Interferences from Th(4+), Mn(2+), Ni(2+) and Cu(2+) ions were masked with ethylene diamine tetra acetic acid (di-sodium salt) (Na(2)EDTA) in the aqueous phase. The developed method has been tested for uranium recovery and estimation in some certified reference materials and environmental samples.