Pentavalent Neptunyl ([O≡Np≡O]<Superscript>+</Superscript>) Cation–Cation Interactions in Aqueous/Polar Organic Mixed-Solvent Media

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O]⁺) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalent linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al³⁺, Sc³⁺, Cr³⁺, Fe³⁺, In³⁺ and \( {\text{UO}}_{2}^{2 + } \)) and the pentavalent neptunyl cation (\( {\text{NpO}}_{2}^{ + } \), whose coordination chemistry is similar to that of \( {\text{AmO}}_{2}^{ + } \) while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. The Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the \( {\text{NpO}}_{2}^{ + } \cdot {\text{Cr}}^{3 + } \) complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.     

Projection methods for equations of the second kind

A class of projection methods, differing from the classical projection methods, is studied for the equation y = f + Ky, where K is a compact linear operator in a Banach space E, and f?E, In these methods K is approximated by a finite-rank operator K_n, which is constructed with the aid of certain projection operators, and which satisfies K_nz = Kz for all z belonging to a chosen subspace U_n ? E. Under certain conditions, it is shown that the convergence of the approximate solution is faster than that of any classical projection method based on the subspace U_n. In an example, U_n is taken to consist of piecewise constant functions, and the projections are so chosen that the method becomes equivalent to a single iteration of a classical method, the collocation method; in this case the error (in the supremum norm) is $\text{O(}\text{1}\text{n}{}^2\text{)}$, compared with $\text{O(}\text{1}\text{n}\text{)}$ for the collocation method.     

Triplet exciton diffusion and phosphorescence quenching in iridium(III)-centered dendrimers

A study of triplet-triplet exciton annihilation and nonradiative decay in films of iridium(III)-centered phosphorescent dendrimers is reported. The average separation of the chromophore was tuned by the molecular structure and also by blending with a host material. It was found that triplet exciton hopping is controlled by electron exchange interactions and can be over 600 times faster than phosphorescence quenching. Nonradiative decay occurs by weak dipole-dipole interactions and is independent of exciton diffusion, except in very thin films (<20 nm) where surface quenching dominates the decay.     

Perdeuterated Conjugated Polymers for Ultralow-Frequency Magnetic Resonance of OLEDs

The formation of excitons in OLEDs is spin dependent and can be controlled by electron-paramagnetic resonance, affecting device resistance and electroluminescence yield. We explore electrically detected magnetic resonance in the regime of very low magnetic fields (<1 mT). A pronounced feature emerges at zero field in addition to the conventional spin- Zeeman resonance for which the Larmor frequency matches that of the incident radiation. By comparing a conventional π-conjugated polymer as the active material to a perdeuterated analogue, we demonstrate the interplay between the zero-field feature and local hyperfine fields. The zero-field peak results from a quasistatic magnetic-field effect of the RF radiation for periods comparable to the carrier-pair lifetime. Zeeman resonances are resolved down to 3.2 MHz, approximately twice the Larmor frequency of an electron in Earth's field. However, since reducing hyperfine fields sharpens the Zeeman peak at the cost of an increased zero-field peak, we suggest that this result may constitute a fundamental low-field limit of magnetic resonance in carrier-pair-based systems. OLEDs offer an alternative solid-state platform to investigate the radical-pair mechanism of magnetic-field effects in photochemical reactions, allowing models of biological magnetoreception to be tested by measuring spin decoherence directly in the time domain by pulsed experiments.     

Simultaneous determination of picogram per gram concentrations of Ba,Pb and Pb isotopes in Greenland ice by thermal ionisation mass spectrometry

A technique has been developed to simultaneously measure picogram per gram concentrations of Ba and Pb by isotope dilution mass spectrometry, as well as Pb isotopic ratios in polar ice by thermal ionisation mass spectrometry. and Pb⁺ ions were employed for these determinations. A calibrated mixture of enriched ²⁰⁵Pb and ¹³⁷Ba was added to the samples providing an accuracy of better than approximately 2% for Pb/Ba element ratio determinations. Interference by molecular ions in the Pb mass spectrum occurred only at ²⁰⁴Pb and ²⁰⁵Pb, but these contributions were negligible in terms of precisions expected on picogram-sized Pb samples. The technique is illustrated with measurements on Greenland firn, using a drill-core section that includes the Laki volcanic eruption of 1783–1784. The data show deviations from the element concentrations indicating volatile metal enrichments, but the Pb isotopic signature of the Laki lava could not be identified.