Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2′,3′-c]phenazine ligands

The complexes (μ₃-L¹/L²)[Ru(acac)₂]₃, acac⁻ = 2,4-pentanedionato, L¹ = 2,3,8,9,14,15-hexachlorodiquinoxalino[2,3-a:2′,3′-c]phenazine and L² = 2,3,8,9,14,15- hexamethyldiquinoxalino[2,3-a:2′,3′-c]phenazine, undergo stepwise one-electron oxidation involving a total of three electrons and stepwise one-electron reduction with three (L²) or four electrons (L¹). All reversibly accessible states were characterized by UV–Vis–NIR spectroelectrochemistry. Oxidation leads to mixed-valent intermediates {(μ₃-L)[Ru(acac)₂]₃}⁺ and {(μ₃-L)[Ru(acac)₂]₃}²⁺ of which the Ru^IIIRu^IIRu^II combinations exhibit higher comproportionation constants K_c than the Ru^IIIRu^IIIRu^II states – in contrast to a previous report for the unsubstituted parent systems {(μ₃-L³)[Ru(acac)₂]₃}^+/2+, L³ = diquinoxalino[2,3-a:2′,3′-c]phenazine. No conspicuous inter-valence charge transfer absorptions were observed for the mixed-valent intermediates in the visible to near-infrared regions. The monocations and monoanions were characterized by EPR spectroscopy, revealing rhombic ruthenium(III) type signals for the former. Electron addition produces ruthenium(II) complexes of the reduced forms of the ligands L, a high resolution EPR spectrum with ¹⁴N and ^35,37Cl hyperfine coupling and negligible g anisotropy was found for {(μ₃-L¹)[Ru(acac)₂]₃}⁻. DFT calculations of (μ₃-L¹)[Ru(acac)₂]₃ confirm several ligand-centered low-lying unoccupied MOs for reduction and several metal-based high-lying occupied MOs for electron withdrawal, resulting in low-energy metal-to-ligand charge transfer (MLCT) transitions.     

Anomalies in quantitative measurement of 40K in natural samples

Journal of Radioanalytical and Nuclear Chemistry - Efficiency calibration by standard materials of known activity is usual protocol for γ-ray spectrometry. In general, 40K activity is measured...     

Production and separation of 111In: an important radionuclide in life sciences: a mini review

¹¹¹In is amongst the frequently used radionuclides in diagnostic nuclear medicine. Therefore its production and subsequent separation chemistry have been widely investigated since late 40s. ¹¹¹In is commonly produced in proton or α-particle induced reactions on cadmium or silver targets. However, in recent past, various heavy ion (⁷Li, ¹¹B, ¹²C etc.) activation routes have been proposed for its production. In this mini review, we have tried to portray the production routes of ¹¹¹In and chemical separation methodologies reported so far in the literature in a concise form. A critical analysis presented in this review will be helpful to select suitable nuclear reaction and radiochemical method to produce high purity ¹¹¹In for applications.     

Cross-spectral density matrix of the far field generated by a blackbody source

An expression is derived for the cross-spectral density matrix, valid in the paraxial region of the far field, generated by a planar blackbody source. With the help of it we determine the spectral degrees of polarization and of cross-polarization of the far field.     

Some remarks on properties for choice functions

In this paper, we present five categories of results by studying the interrelationships between properties for choice functions. The first category is about the localization assumption. The second category is about the relative egalitarian solution. The third category provides an axiomatic characterization of the equal loss solution. The fourth and fifth categories consist of lexicographic extensions of the equal loss and relative egalitarian solutions respectively. This revised version was published online in June 2006 with corrections to the Cover Date.