N. S. Dalal

Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture

Multiferroic behavior in perovskite-related metal-organic frameworks of general formula [(CH(3))(2)NH(2)]M(HCOO)(3), where M = Mn, Fe, Co, and Ni, is reported. All four compounds exhibit paraelectric-antiferroelectric phase transition behavior in the temperature range 160-185 K (Mn: 185 K, Fe: 160 K; Co: 165 K; Ni: 180 K); this is associated with an order-disorder transition involving the hydrogen bonded dimethylammonium cations. On further cooling, the compounds become canted weak ferromagnets below 40 K. This research opens up a new class of multiferroics in which the electrical ordering is achieved by means of hydrogen bonding.

Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture.

[(CH3)2NH2]Zn(HCOO)3, 1, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the dimethyl ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temperature. X-ray powder diffraction, dielectric constant, and specific heat data show that 1 undergoes an order-disorder phase transition on cooling below 156 K. We present evidence that this is a classical paraelectric to antiferroelectric phase transition that is driven by ordering of the hydrogen atoms. This sort of electrical ordering associated with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.

On the hydroxyl radical formation in the reaction between hydrogen peroxide and biologically generated chromium(V) species.

Electron spin resonance (ESR) measurements on solutions and isolated powders provide direct evidence for the involvement of Cr(V) species in the reduction of Cr(VI) by NAD(P)H. ESR analysis of an isolated Cr(V)-NAD(P)H solid yields g parallel = 1.9831 and g perpendicular = 1.9772, indicating that the unpaired electron occupies the dz2 orbital of the Cr(V) ion, with square-pyramidal geometry. Addition of hydrogen peroxide (H2O2) to the NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) species and generates hydroxyl (.OH) radicals. The .OH radicals were detected via ESR spin trapping, employing 5,5-dimethyl-1-pyrroline-N-oxide and alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone as spin traps. The dependence of Cr(V) and .OH radical formation on the H2O2 and Cr(VI) concentrations indicates that the Cr(V) species react with H2O2 to generate the .OH radicals. Similar results were obtained by using various diols (arabinose, cellobiose, FAD, fructose, glyceraldehyde, ribose, and tartaric acid), alpha-hydroxycarboxylic acids, and glutathione. Investigations with superoxide dismutase showed no significant participation of O2- in the generation of .OH radicals. These results thus indicate that the Cr(V) complexes, produced in the reduction of Cr(VI) by cellular reductants, react with H2O2 to generate .OH radicals, which might be initiators of the primary events in the Cr(VI) cytotoxicity.

Chromium (V) and hydroxyl radical formation during the glutathione reductase-catalyzed reduction of chromium (VI)

Electron spin resonance measurements provide evidence for the formation of long-lived Cr(V) intermediates in the reduction of Cr(VI) by glutathione reductase in the presence of NADPH and for the hydroxyl radical formation during the glutathione reductase catalyzed reduction of Cr(VI). Hydrogen peroxide suppresses Cr(V) and enhances the formation of hydroxyl radicals. Thus Cr(V) intermediates catalyze generation of hydroxyl radicals from hydrogen peroxide through a Fenton-like reaction. Thus the mechanism of Cr(VI) toxicity might involve the interaction between macromolecules and the hydroxyl radicals.

Apparent copper(II)-accelerated azide-alkyne cycloaddition.

Cu(II) salts accelerate azide-alkyne cycloaddition reactions in alcoholic solvents without reductants such as sodium ascorbate. Spectroscopic observations suggest that Cu(II) undergoes reduction to catalytic Cu(I) species via either alcohol oxidation or alkyne homocoupling, or both, during an induction period. The reactions involving 2-picolylazide are likely facilitated by its chelation to Cu(II). The highly exothermic reaction between 2-picolylazide and propargyl alcohol completes within 1-2 min in the presence of as low as 1 mol % Cu(OAc)(2).

Mechanism of the order–disorder phase transition, and glassy behavior in the metal-organic framework [(CH3)2NH2]Zn(HCOO)3

Transitions associated with orientational order–disorder phenomena are found in a wide range of materials and may have a significant impact on their properties. In this work, specific heat and 1H NMR measurements have been used to study the phase transition in the metal-organic framework (MOF) compound [(CH3)2NH2]Zn(HCOO)3. This compound, which possesses a perovskite-type architecture, undergoes a remarkable order–disorder phase transition at 156 K. The (DMA+) cationic moieties that are bound by hydrogen bonds to the oxygens of the formate groups (N─H⋯O ∼ 2.9 Å) are essentially trapped inside the basic perovskite cage architecture. Above 156 K, it is the orientations of these moieties that are responsible for the disorder, as each can take up three different orientations with equal probability. Below 156 K, the DMA+ is ordered within one of these sites, although the moiety still retains a considerable state of motion. Below 40 K, the rotational motions of the methyl groups start to freeze. As the temperature is increased from 4 K in the NMR measurements, different relaxation pathways can be observed in the temperature range approximately 65–150 K, as a result of a “memory effect.” This dynamic behavior is characteristic of a glass in which multiple states possess similar energies, found here for a MOF. This conclusion is strongly supported by the specific heat data.

Evidence for a Fenton-type mechanism for the generation of .OH radicals in the reduction of Cr(VI) in cellular media.

Electron spin resonance (ESR) spectroscopy has been employed to examine the role of tetraperoxochromate (V) ions (CrO3-8) and other Cr(V) species in the generation of hydroxyl (OH) radicals in the reaction of Cr(VI) with H2O2 in biological media. In contrast to earlier suggestions, the present ESR studies using crystalline K3CrO8 as a source of CrO3-8 show that decomposition of CrO3-8 in water or in H2O2 does not generate significant amounts of OH radicals. Addition of NADH to a solution containing CrO3-8 yields a Cr(V)-NADH complex, which readily reacts with H2O2 to generate OH radicals. Similar results obtained from several other biological reductants, including vitamin B2, indicate that a vacant coordination site on a Cr(V) complex facilitates its reaction with H2O2 to generate .OH radicals. We thus suggest that in biological media, reaction [3] instead of [1] or [2] is the major pathway for the .OH radical generation: [formula, see text]

A Planar {Mn19(OH)12}26+ Unit Incorporated in a 60‐Tungsto‐6‐Silicate Polyanion

Polyoxometalates (POMs) are discrete metal–oxo anions of early transition-metals in high oxidation states (e.g. W, Mo, V) and they are usually synthesized in aqueous, acidic medium. Most classical POMs are based on edgeand corner-shared MO6 octahedra. However, the recently discovered POM subclass of noble metalates comprises linked square-planar MO4 units (M = Pd , Au). Lacunary (vacant) POMs can be considered as inorganic, multidentate ligands, and hence they are good candidates for the encapsulation of large, multinuclear dand f-block metal–oxo fragments, sometimes resulting in compounds with interesting magnetic properties. A pioneering result in this area was the synthesis of [Mn12(CH3COO)16(H2O)4O12] (Mn12) by Lis in 1980, which was shown to exhibit single-molecule magnet (SMM) behavior by Gatteschi s group 13 years later. During the past two decades many high-nuclearity, transition-metal based, coordination complexes with interesting electronic and magnetic properties have been prepared. High-nuclearity manganese complexes have been amongst the most studied in this class, and there are examples containing up to 84 manganese ions. 6] To date there are only a few high-nuclearity manganese– oxo-containing POMs, such as {[XW9O34]2[Mn III 4Mn II 2O4(H2O)4]} 12 (X = Si, Ge) and [Mn13Mn O12(PO4)4(PW9O34)4] 31 . Herein we report the synthesis and structure as well as the magnetic and electrochemical properties of a 19 manganese(II) center containing 60-tungsto-6-silicate, [Mn19(OH)12(SiW10O37)6] 34 (1), which was isolated as a hydrated sodium salt, Na34[Mn19(OH)12(SiW10O37)6]·115H2O (Na-1). Single-crystal X-ray diffraction revealed that polyanion 1 consists of a cationic {Mn19(OH)12} 26+ (Mn19) assembly stabilized by six dilacunary [a-SiW10O37] 10 units resulting in a structure with S6 point-group symmetry (Figure 1, top). To the best of our knowledge, 1 is the highest nuclearity manganesecontaining POM known to date. All 19 Mn ions lie in the same plane forming a hexagonal structure based on edgeshared MnO6 octahedra. The Mn II ions in Mn19 are connected by a total of twelve m3-hydroxo bridges, as determined by bond valence sum (BVS) calculations (Supporting Information, Table S1). The discrete Mn19 nanosheet (Figure 1, bottom) is held in place by six dilacunary [a-SiW10O37] 10

Nucleation Process in the Cavity of a 48‐Tungstophosphate Wheel Resulting in a 16‐Metal‐Centre Iron Oxide Nanocluster

The 16-Fe(III)-containing 48-tungsto-8-phosphate [P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)](20-) (1) has been synthesised and characterised by IR and ESR spectroscopy, TGA, elemental analyses, electrochemistry and susceptibility measurements. Single-crystal X-ray analyses were carried out on Li(4)K(16)[P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)]66 H(2)O2 KCl (LiK-1, orthorhombic space group Pnnm, a=36.3777(9) A, b=13.9708(3) A, c=26.9140(7) A, and Z=2) and on the corresponding mixed sodium-potassium salt Na(9)K(11)[P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)].100 H(2)O (NaK-1, monoclinic space group C2/c, a=46.552(4) A, b=20.8239(18) A, c=27.826(2) A, beta=97.141(2) degrees and Z=4). Polyanion 1 contains--in the form of a cyclic arrangement--the unprecedented {Fe(16)(OH)(28)(H(2)O)(4)}(20+) nanocluster, with 16 edge- and corner-sharing FeO(6) octahedra, grafted on the inner surface of the crown-shaped [H(7)P(8)W(48)O(184)](33-) (P(8)W(48)) precursor. The synthesis of 1 was accomplished by reaction of different iron species containing Fe(II) (in presence of O(2)) or Fe(III) ions with the P(8)W(48) anion in aqueous, acidic medium (pH approximately 4), which can be regarded as an assembly process under confined geometries. One fascinating aspect is the possibility to model the uptake and release of iron in ferritin. The electrochemical study of 1, which is stable from pH 1 through 7, offers an interesting example of a highly iron-rich cluster. The reduction wave associated with the Fe(III) centres could not be split in distinct steps independent of the potential scan rate from 2 to 1000 mV s(-1); this is in full agreement with the structure showing that all 16 iron centres are equivalent. Polyanion 1 proved to be efficient for the electrocatalytic reduction of NO(x), including nitrate. Magnetic and variable frequency EPR measurements on 1 suggest that the Fe(III) ions are strongly antiferromagnetically coupled and that the ground state is tentatively spin S=2.

On the mechanism of the chromate reduction by glutathione: ESR evidence for the glutathionyl radical and an isolable Cr(V) intermediate

With a view of elucidating the role of glutathione (GSH) in the biochemical pathways of the chromate-exposure related carcinogenesis, we carried out electron spin resonance (ESR) spectroscopic investigations of the chromate-GSH redox reactions. The ESR measurements, employing spin-traps, provide evidence for the involvement of the glutathione (GS) radical, as well as an isolable Cr(V)-glutathione intermediate. These results indicate a new mechanism for the reduction of chromate by GSH in in vitro cellular environment and help understand the (unexpected) increase in Cr(VI)-induced DNA strand breaks at elevated GSH levels.