Iridium containing honeycomb Delafossites by topotactic cation exchange.

We report the structure and magnetic properties of two new iridium-based honeycomb Delafossite compounds, Cu3NaIr2O6 and Cu3LiIr2O6, formed by a topotactic cation exchange reaction. The starting materials Na2IrO3 and Li2IrO3, which are based on layers of IrO6 octahedra in a honeycomb lattice separated by layers of alkali ions, are transformed to the title compounds by a topotactic exchange reaction through heating with CuCl below 450 °C; higher temperature reactions cause decomposition. The new compounds display dramatically different magnetic behavior from their parent compounds - Cu3NaIr2O6 has a ferromagnetic like magnetic transition at 10 K, while Cu3LiIr2O6 retains the antiferromagnetic transition temperature of its parent compound but displays significantly stronger dominance of antiferromagnetic coupling between spins. These results reveal that a surprising difference in the magnetic interactions between the magnetic Ir ions has been induced by a change in the non-magnetic interlayer species. A combination of neutron and X-ray powder diffraction is used for the structure refinement of Cu3NaIr2O6 and both compounds are compared to their parent materials.

Tuning Sodium Ion Conductivity in the Layered Honeycomb Oxide Na(3-x)Sn(2-x)Sb(x)NaO6.

A series of compounds with the composition Na(3-x)Sn(2-x)Sb(x)NaO6 (x = 0.0, 0.2, 0.4, 0.6, 0.7, 0.8, 0.9, and 1.0) has been prepared by solid-state reaction and characterized by powder X-ray diffraction, neutron diffraction (for x = 0.0), and impedance spectroscopy. The compounds have a layered structure derived from that of α-NaFeO2, with alternating Na3 planes and NaSn2O6 slabs with honeycomb in-plane ordering. The structure of the parent compound, Na2SnO3, has been determined as a two-layer honeycomb in monoclinic space group C2/c. Due to charge neutrality requirements, the substitution of Sb(5+) for Sn(4+) creates sodium site vacancies that facilitate high sodium ion mobility. A decrease in layer stacking disorder is also observed. The conductivity increases linearly with x and has a maximum at x = 0.8 (1.43 × 10(-3) S/cm at 500 °C with suboptimal sample densities). This material may be of interest as a solid Na ion electrolyte.

Rhombohedral polytypes of the layered honeycomb delafossites with optical brilliance in the visible.

We report the synthesis of the Delafossite honeycomb compounds Cu3Ni2SbO6 and Cu3Co2SbO6 via a copper topotactic reaction from the layered α-NaFeO2-like precursors Na3Ni2SbO6 and Na3Co2SbO6. The low-temperature exchange reaction exclusively produces the rhombahedral 3R polytype subcell, whereas only the hexagonal 2H polytype subcell has been made by conventional synthesis. The thus-synthesized 3R variants are visually striking; they are bright lime-green (Ni variant) and terracotta-orange (Co variant), while both of the conventionally synthesized 2H variants have a burnt-red color. The new structures are characterized by powder X-ray diffraction and Rietveld analysis as well as magnetic susceptibility, X-ray photoelectron spectroscopy (XPS), and diffuse-reflectance optical spectroscopy. Using thermogravimetric analysis, we identify a second order 3R → 2H phase transition as well as a first-order structural transition associated with rearrangement of the honeycomb stacking layers. The optical absorbance spectra of the samples show discrete edges that correlate well to their visual colors. Exposing Cu3Ni2SbO6 to O2 and heat causes the sample to change color. XPS confirms the presence of Cu(2+) in these samples, which implies that the difference in color between the polytypes is due to oxygen intercalation resulting from their different synthetic routes.

Structure and magnetic properties of the spin-1/2-based honeycomb NaNi2BiO(6-δ) and its hydrate NaNi2BiO(6-δ)·1.7H2O.

We present the structure and magnetic properties of the honeycomb anhydrate NaNi2BiO6-δ and its monolayer hydrate NaNi2BiO6-δ·1.7H2O, synthesized by deintercalation of the layered α-NaFeO2-type honeycomb compound Na3Ni2BiO6. The anhydrate adopts ABAB-type oxygen packing and a one-layer hexagonal unit cell, whereas the hydrate adopts an oxygen packing sequence based on a three-layer rhombohedral subcell. The metal-oxide layer separations are 5.7 Å in the anhydrate and 7.1 Å in the hydrate, making the hydrate a quasi 2-D honeycomb system. The compounds were characterized through single crystal diffraction, powder X-ray diffraction, thermogravimetric analysis, and elemental analysis. Temperature-dependent magnetic susceptibility measurements show both to have negative Weiss temperatures (-18.5 and -14.6 K, respectively) and similar magnetic moments (2.21 and 2.26 µB/Ni, respectively), though the field-dependent magnetization and heat capacity data suggest subtle differences in their magnetic behavior. The magnetic moments per Ni are relatively high, which we suggest is due to the presence of a mixture of Ni(2+) and Ni(3+) caused by oxygen vacancies.

Formation of the tetranuclear, tetrakis-terminal-imido Mn4(IV)(N(t)Bu)8 cubane cluster by four-electron reductive elimination of (t)BuN=N(t)Bu. The role of the s-block ion in stabilization of high-oxidation state intermediates.

Mn4(IV)(µ3-N(t)Bu)4(N(t)Bu)4 is obtained from a previously reported asymmetric Mn(IV/V)-Li-(NR)(N) cluster by the removal of Li from the starting cluster by ion metathesis, which triggers reductive elimination of azo-tert-butane to give a tetranuclear heterocubane cluster.

Phase range of the type-I clathrate Sr8Al(x)Si(46-x) and crystal structure of Sr8Al10Si36.

Samples of the type-I clathrate Sr(8)Al(x)Si(46-x) have been prepared by direct reaction of the elements. The type-I clathrate structure (cubic space group Pm3n) which has an Al-Si framework with Sr(2+) guest atoms forms with a narrow composition range of 9.54(6) ≤ x ≤ 10.30(8). Single crystals with composition A(8)Al(10)Si(36) (A = Sr, Ba) have been synthesized. Differential scanning calorimetry (DSC) measurements provide evidence for a peritectic reaction and melting point at ∼1268 and ∼1421 K for Sr(8)Al(10)Si(36) and Ba(8)Al(10)Si(36), respectively. Comparison of the structures reveals a strong correlation between the 24k-24k framework sites distances and the size of the guest cation. Electronic structure calculation and bonding analysis were carried out for the ordered models with the compositions A(8)Al(6)Si(40) (6c site occupied completely by Al) and A(8)Al(16)Si(30) (16i site occupied completely with Al). Analysis of the distribution of the electron localizability indicator (ELI) confirms that the Si-Si bonds are covalent, the Al-Si bonds are polar covalent, and the guest and the framework bonds are ionic in nature. The Sr(8)Al(6)Si(40) phase has a very small band gap that is closed upon additional Al, as observed in Sr(8)Al(16)Si(30). An explanation for the absence of a semiconducting "Sr(8)Al(16)Si(30)" phase is suggested in light of these findings.

Neutron diffraction study of the type I clathrate Ba8Al(x)Si(46-x): site occupancies, cage volumes, and the interaction between the guest and the host framework.

Samples with the type I clathrate structure and composition Ba(8)Al(x)Si(46-x), where x = 8, 10, 12, 14, and 15, were examined by neutron powder diffraction at 35 K. The clathrate type I structure contains Ba cations as guests in a framework derived from tetrahedrally coordinated Al/Si atoms. The framework is made up of five- and six-membered rings that form dodecahedral and tetrakaidecahedral cages. The change in distances between tetrahedral sites across the series is used to develop a model for the mixed Al/Si occupancy observed in the framework. The calculated volumes of the cages that contain the Ba atoms display a linear increase with increasing Al composition. In the smaller dodecahedral cages, the Ba atomic displacement parameter is symmetry constrained to be isotropic for all compositions. In the larger tetrakaidecahedral cages, the anisotropic atomic displacement of the Ba atom depends upon the composition: the displacement is perpendicular (x = 8) and parallel (x = 15) to the six-membered ring. This difference in direction of the displacement parameter is attributed to interaction with the Al in the framework and not to the size of the cage volume as x increases from 8 to 15. The influence of the site occupation of Al in the framework on displacement of the cation at the 6d site is demonstrated.

One-electron oxidation of ruthenocene: reactions of the ruthenocenium ion in gentle electrolyte media.

The electrochemical oxidation of ruthenocene, RuCp(2) (Cp = eta(5)-C(5)H(5)), 1, has been studied in dichloromethane using a supporting electrolyte containing either the [B(C(6)F(5))(4)](-) (TFAB) or the [B(C(6)H(3)(CF(3))(2))(4)](-) (BArF(24)) counteranion. A quasi-Nernstian process was observed in both cases, with E(1/2) values of 0.41 and 0.57 V vs FeCp(2) in the respective electrolyte media. The ruthenocenium ion 1(+) equilibrates with a metal-metal bonded dimer [Ru(2)Cp(4)](2+), 2(2+), that is increasingly preferred at low temperatures. Dimerization equilibrium constants determined by digital simulation of cyclic voltammetry (CV) curves were in the range of 10(2)-10(4) M(-1) at temperatures of 256 to 298 K. Near room temperature, and particularly when BArF(24) is the counteranion, the dinuclear species [Ru(2)Cp(2)(sigma:eta(5)-C(5)H(4))(2)] (2+), 3(2+), in which each metal is sigma-bonded to a cyclopentadienyl ring, was the preferred electrolytic oxidation product. Cathodic reduction of 3(2+) regenerated ruthenocene. The two dinuclear products, 2(2+) and 3(2+), were characterized by (1)H NMR spectroscopy on anodically electrolyzed solutions of 1 at low temperatures in CD(2)Cl(2)/[NBu(4)][BArF(24)]. The variable temperature NMR behavior of these solutions showed that 3(2+) and 2(2+) take part in a thermal equilibrium, the latter being dominant at the lowest temperatures. Ruthenocene hydride, [1-H](+), was also identified as being present in the electrolysis solutions. The oxidation of ruthenocene is shown to be an inherent one-electron process, giving a ruthenocenium ion which is highly susceptible to reactions that allow it to regain an 18-electron configuration. In a dry non-donor solvent, and in the absence of nucleophiles, this electronic configuration is attained by self-reactions involving formation of Ru-Ru or Ru-C bonds. The present data offer a mechanistic explanation for the previously described results on the chemical oxidation of osmocene (Droege, M.W.; Harman, W.D.; Taube, H. Inorg. Chem. 1987, 26, 1309) and are relevant to the manner in which sigma:eta(5)-C(5)H(4)-complexes of other second and third-row metals are formed.