Dilacunary decatungstates functionalized by organometallic ruthenium(II), [{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-XW10O36)]4- (X = Si, Ge)

The benzene-Ru(II)-supported dilacunary decatungstosilicate [{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-SiW10O36)]4- and the isostructural decatungstogermanate [{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-GeW10O36)]4- have been synthesized and characterized by multinuclear solution NMR, IR, elemental analysis, and electrochemistry. Single-crystal X-ray analysis was carried out on K4[{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-SiW10O36)].9H2O (K-1), which crystallizes in the orthorhombic system, space group Pmn2(1), with a = 13.6702(3) A, b = 16.2419(4) A, c = 12.1397(2) A, and Z = 2, and on K4[{Ru(C6H6)(H2O)}{Ru(C6H6)}(gamma-GeW10O36)].7H2O (K-2), which also crystallizes in the orthorhombic system, space group Pmn2(1), with a = 13.6684(12) A, b = 16.297(2) A, c = 12.1607(13) A, and Z = 2. Polyanions 1 and 2 consist of a Ru(C6H6)(H2O) group and a Ru(C6H6) group linked to a dilacunary (gamma-XW10O36) Keggin fragment resulting in an assembly with idealized Cs symmetry. The Ru(C6H6)(H2O) group is bound at the lacunary polyanion site via two Ru-O(W) bonds, whereas the Ru(C6H6) group is bound on the side via three Ru-O(W) bonds. Polyanions 1 and 2 were synthesized in aqueous acidic medium at pH 2.5 by the reaction of [Ru(C6H6)Cl2]2 with [gamma-SiW10O36]8- and [gamma-GeW10O36]8-, respectively. The formal potentials are roughly the same for the first W waves of 1 and 2. However, important differences appear for the second W waves. These observations indicate different acid-base properties for the reduced forms of 1 and 2. Three oxidation processes were detected: the oxidation of the Ru center is followed first by irreversible electrocatalytic processes of the Ru-benzene moiety and then of the electrolyte. Comparison of this behavior with that of the precursor reagent, [Ru(C6H6)Cl2]2, was useful to understand the main oxidation processes. A ligand substitution reaction was observed upon addition of dimethyl sulfoxide (dmso) to 1, 2, or [Ru(C6H6)Cl2]2. This reaction facilitates substantially the oxidation of the Ru center. The dmso was oxidized with large electrocatalytic currents more efficiently in the presence of 1 and 2 than with [Ru(C6H6)Cl2]2.     

Strong ferromagnetic exchange couplings in copper(II) and nickel(II) complexes with a paramagnetic tridentate chelate ligand, 2,2'-bipyridin-6-yl tert-butyl nitroxide

A paramagnetic ligand 6bpyNO (2,2'-bipyridin-6-yl tert-butyl nitroxide) is a newcomer in the field of metal-radical hybrid magnetic materials. Complexes [CuII(6bpyNO)Cl2] and [NiII(6bpyNO)2](PF6)2 having highly planar chelate rings showed considerably strong ferromagnetic exchange couplings J/kB = 202 and 192 K, respectively, across the direct radical oxygen coordination bonds (the spin Hamiltonian is defined as -2JSi.Sj).     

Full-parallax three-dimensional display based on light field reproduction

Optical Review - Light field displays can display three-dimensional (3D) images with smooth motion parallax without the use of special glasses, by reproducing light ray information from objects....     

{W48} ring opening: Fe16-containing, Ln4-stabilized 49-tungsto-8-phosphateopen wheel [Fe16O2(OH)23(H2O)9(P8W49O189)Ln4(H2O)20]11-

Wheely: For the first time and very unexpectedly, a rupture of the very stable {P(8)W(48)} wheel was observed in aqueous solution at pH?4 and 80?°C in the presence of Fe(III), Eu(III)/Gd(III), and H(2)O(2). This inorganic ring opening is unprecedented in polyoxometalate chemistry.     

Facile formation of five-membered N-heterocyclic zirconacycloallenoids

The reaction of η(2)-iminozirconocene chloride complexes with trimethylsilylethynyl lithium leads to rapid C-C coupling at room temperature to yield the corresponding five-membered aza-zirconacycloallenoids. Such compounds were also obtained by trapping of in situ generated zirconocene with alkynyl imines.     

Structural Transitions from Triangular to Square Molecular Arrangements in the Quasi-One-Dimensional Molecular Conductors (DMEDO-TTF)(2)XF(6) (X = P, As, and Sb)

A series of quasi-one-dimensional molecular conductors (DMEDO-TTF)(2)XF(6) (X = P, As, and Sb), where DMEDO-TTF is dimethyl(ethylenedioxy)tetrathiafulvalene, undergo characteristic structural transitions in the range of 130-195 K for the PF(6) salt and 222-242 K for the AsF(6) salt. The dramatic structural transition is induced by the order of the ethylenedioxy moiety, and the resulting anion rotation leads to the reconstruction of the H···F interaction between the methyl groups and the anions. The unique hydrogen bonds play a crucial role in the transition. As a result, the molecular packing is rearranged entirely; the high-temperature molecular stacks with an ordinary quasi-triangular molecular network transforms to a quasi-square-like network, which has never been observed among organic conductors. Nonetheless, the low-temperature phase exhibits a good metallic conductivity as well, so the transition is a metal-metal (MM) transition. The resistivity measured along the perpendicular direction to the conducting ac-plane (ρ(⊥)) and the calculation of the Fermi surface demonstrate that the high-temperature metal phase is a one-dimensional metal, whereas the low-temperature metal phase has considerable interchain interaction. In the SbF(6) salt, a similar structural transition takes place around 370 K, so that the quasi-square-like lattice is realized even at room temperature. Despite the largely different MM transition temperatures, all these salts undergo metal-insulator (MI) transitions approximately at the same temperature of 50 K. The low-temperature insulator phase is nonmagnetic, and the reflectance spectra suggest the presence of charge disproportionation with small charge difference (0.14).     

Synthesis of (zinc(II) phthalocyanine)-containing cellulose derivative using phthalocyanine-ring formation reaction

2,3-Di-O-myristyl-6-O-(zinc(II) phthalocyaninyl) cellulose (5) was synthesized from cellulose (1) by five reaction steps via 6-O-(3′,4′-dicyanophenyl)-2,3-di-O-myristyl cellulose (4). The key reaction was phthalocyanine-ring formation on a cellulose backbone, that is, the reaction of compound 4 with o-phthalodinitrile in the presence of hexamethyldisilazane and zinc acetate in DMF afforded to compound 5 in 35.4 % yield. Consequently, the degree of substitution with phthalocyanine moieties of compound 5 was 0.38. The LB monolayer film of compound 5 on an indium tin oxide (ITO) electrode was found to show photocurrent generation performance at 680 nm.     

Reporting of quantitative oxygen mapping in EPR imaging

Oxygen maps derived from electron paramagnetic resonance spectral-spatial imaging (EPRI) are based upon the relaxivity of molecular oxygen with paramagnetic spin probes. This technique can be combined with MRI to facilitate mapping of pO(2) values in specific anatomic locations with high precision. The co-registration procedure, which matches the physical and digital dimensions of EPR and MR images, may present the pO(2) map at the higher MRI resolution, exaggerating the spatial resolution of oxygen, making it difficult to precisely distinguish hypoxic regions from normoxic regions. The latter distinction is critical in monitoring the treatment of cancer by radiation and chemotherapy, since it is well-established that hypoxic regions are three or four times more resistant to treatment compared to normoxic regions. The aim of this article is to describe pO(2) maps based on the intrinsic resolution of EPRI. A spectral parameter that affects the intrinsic spatial resolution of EPRI is the full width at half maximum (FWHM) height of the gradient-free EPR absorption line in frequency-encoded imaging. In single point imaging too, the transverse relaxation times (T(2)(?)) limit the resolution since the signal decays by exp(-t(p)/T(2)(?)) where the delay time after excitation pulse, t(p), is related to the resolution. Although the spin densities of two point objects may be resolved at this separation, it is inadequate to evaluate quantitative changes of pO(2) levels since the linewidths are proportionately affected by pO(2). A spatial separation of at least twice this resolution is necessary to correctly identify a change in pO(2) level. In addition, the pO(2) values are blurred by uncertainties arising from spectral dimensions. Blurring due to noise and low resolution modulates the pO(2) levels at the boundaries of hypoxic and normoxic regions resulting in higher apparent pO(2) levels in hypoxic regions. Therefore, specification of intrinsic resolution and pO(2) uncertainties are necessary to interpret digitally processed pO(2) illustrations.     

Chiroptical properties of an alternatingly functionalized cellotriose bearing two porphyrin groups

Right-handedness derived from bisporphyrins attached to a cellotriose backbone at O-6 and O'-6 positions is revealed for the first time. This cellotriose is proposed as a model of alternatingly functionalized cellulosics, which have promising properties for applications in optoelectronics and molecular receptors owing to the chirality and rigid backbone effects.