Discrimination of Chiral and Helical Contributions to Raman Scattering of Liquid Crystals Using Vortex Beams.

We use vortex photon fields with orbital and spin angular momentum to probe chiral fluctuations within liquid crystals. In the regime of iridescence with a well-defined pitch length of chirality, we find low energy Raman scattering that can be decomposed into helical and chiral components depending on the scattering vector and the topological charge of the incident photon field. Based on the observation of an anomalous dispersion we attribute quasielastic scattering to a transfer of angular momenta to rotonlike quasiparticles. The latter are due to a competition of short-range repulsive and long-range dipolar interactions. Our approach using a transfer of orbital angular momentum opens up an avenue for the advanced characterization of chiral and optically active devices and materials.

Reactivity of FeMoO4 in CsCl Fluxes and Formation of the Salt-Inclusion Type of Compounds.

The reactivity of FeMoO4 in CsCl fluxes has been investigated by thermal analysis and chemical reactions in evacuated silica ampules. The products have been characterized by ex situ X-ray diffraction methods. Metathesis reactions involving CsCl lead to the formation of Cs2Fe2(MoO4)3 and the salt adduct Cs2FeCl4·CsCl. A side reaction has been observed, which is associated with a decomposition of [MoO4]2- in CsCl fluxes yielding Cs2Mo2O7·CsCl, which contains the rare pyromolybdate anion, [Mo2O7]2-, located in the center of a ∞2[CsCl] hetero-honeycomb arrangement. This salt-inclusion type of compound has been studied further in terms of its formation starting from Cs2MoO4, MoO3, and CsCl. The intermediate adduct phase, Cs2MoO4·MoO3, contains uncharged ∞1[MoO2O2/2] chains that react with CsCl at elevated temperatures to Cs2Mo2O7·CsCl. Furthermore, the site preference for alkaline-metal cations (K+, Rb+, and Cs+) has been evaluated for a mixed substitution series. In accordance with the Pearson concept, the polarizability of the respect cation outweighs any size differences for the occupancy of the salt-intergrowth motif, the honeycomb part of the structure.

Panchromatic Absorption and Oxidation of an Iron(II) Spin Crossover Complex.

In order to expand and exploit the useful properties of d6-iron(II) and d5-iron(III) complexes in potential magnetic, photophysical, or magnetooptical applications, crucial ligand-controlled parameters are the ligand field strength in a given coordination mode and the availability of suitable metal and ligand frontier orbitals for charge-transfer processes. The push-pull ligand 2,6-diguanidylpyridine (dgpy) features low-energy π* orbitals at the pyridine site and strongly electron-donating guanidinyl donors combined with the ability to form six-membered chelate rings for optimal metal-ligand orbital overlap. The electronic ground states of the pseudo-octahedral d6- and d5-complexes mer-[Fe(dgpy)2]2+, cis-fac-[Fe(dgpy)2]2+, and mer-[Fe(dgpy)2]3+ as well as their charge-transfer (CT) and metal-centered (MC) excited states are probed by variable temperature UV/vis absorption, NMR, EPR, and Mössbauer spectroscopy, magnetic susceptibility measurements at variable temperature as well as quantum chemical calculations.

Phase Trapping in Multistep Spin Crossover Compound.

The dimeric motif is the smallest unit for two interacting spin centers allowing for systematic investigations of cooperative interactions. As spin transition compounds, dinuclear complexes are of particular interest, since they potentially reveal a two-step spin crossover (SCO), switching between the high spin-high spin [HS-HS], the high spin-low spin [HS-LS], and the low spin-low spin [LS-LS] states. Herein, we report the synthesis and characterization of six dinuclear iron(II) complexes [FeII2(µ2-L1)2](BF4)4 (C1), [FeII2(µ2-L1)2](ClO4)4 (C2), [FeII2(µ2-L1)2](F3CSO3)4 (C3), [FeII2(µ2-L2)2](BF4)4 (C4), [FeII2(µ2-L2)2](BF4)4 (C5), and [FeII2(µ2-L2)2](BF4)4 (C6), based on the 1,3,4-thiadiazole bridging motif. The two novel bis-tridentate ligands (L1 = 2,5-bis{[(1H-imidazol-2-ylmethyl)-amino]-methyl}-1,3,4-thiadiazole and L2 = 2,5-bis{[(thiazol-2-ylmethyl)-amino]-methyl}-1,3,4-thiadiazole) were employed in the presence of iron(II) salts with the different counterions. Upon varying ligands and counterions, we were able to change the magnetic properties of the complexes from a temperature-independent [HS-HS] spin state over a one-step spin transition toward a two-step SCO. When cooled slowly from room temperature, the two-step SCO goes along with two distinct phase transitions, and in the intermediate mixed [HS-LS] state distinct HS/LS pairs can be identified unambiguously. In contrast, rapid cooling precludes a crystallographically observable phase transition. For the mixed [HS-LS] state Mössbauer spectroscopy confirms a statistical (random) orientation of adjacent [HS-LS]·[HS-LS]·[HS-LS] chains.

A Mixed-Valent Iron (II/III) Diamond Chain with Single-Ion Anisotropy.

The geometrically frustrated diamond spin chain system has yielded materials with a diversity of interesting magnetic properties but is predominantly limited to compounds with single-spin components. Here, we report the compound [(CH3)2NH2]6[FeIII4FeII2(µ3-O)2(µ3-OH)2(µ3-SO4)8] (1), which features the mixed-valent iron(II/III) diamond chain: ∞[FeIII-(FeIII)2-FeIII-(FeII)2]. 57Fe Mössbauer spectroscopy shows that two-thirds of the total spins in the ∞[FeIII4FeII2] diamond chain are spin-5/2 (high-spin FeIII), while the remaining one-third are spin-2 (high-spin FeII). To date, 1 is the only diamond-chain compound composed of more than one type of dimer, namely, (FeIII)2 and (FeII)2. On the basis of temperature-dependent 57Fe Mössbauer spectroscopy data, an alternating noncollinear 90° magnetic structure is proposed. Both the (FeIII)2 and (FeII)2 dimers are antiferromagnetically coupled and align in the direction along the chain axis ≈ [010], whereas the moments of the bridging FeIII monomers are oriented orthogonally. The spin canting, arising from the anisotropy of the FeII ions, leads to ferrimagnetic ordering at low temperatures.

Screw- Type Motion and Its Impact on Cooperativity in BaNa2Fe[VO4]2.

BaNa2Fe[VO4]2 contains a Jahn-Teller active ion (FeII, 3d6, high-spin) in an octahedral coordination. On the basis of a combination of temperature-dependent X-ray diffraction and Mössbauer and Raman spectroscopies, we demonstrate the coupling of lattice dynamics with the electronic ground state of FeII. We identify three lattice modes combined to an effective canted screw- type motion that drives the structural transition around room temperature from the high-temperature ( P3̅) via intermediate phases to the low-temperature phase ( C2/ c). The dynamics of the electronic ground state of Fe(II) are evident from Mössbauer data with signatures of a motion-narrowed doublet above 320 K, a gradual evolution of the 5Eg electronic state below 293 K, and finally the signature of the thermodynamically preferred orbitally nondegenerate ground state (5Ag) of Fe(II) below 100 K. The continuous nature of the transition is associated with the temperature-dependent phonon parameters derived from Raman spectroscopy, which point out the presence of strong electron-phonon coupling in this compound. We present a microscopic mechanism and evaluate the collective component leading to the structural phase transition.

BaMn9[VO4]6(OH)2: a unique canted antiferromagnet with a chiral "paddle-wheel" structural feature.

BaMn(9)[VO(4)](6)(OH)(2) was synthesized by hydrothermal methods. We evaluated the crystal structure based on the two possible space groups P2(1)3 and Pa3̅ [a = 12.8417(2) Å] using single-crystal and powder X-ray diffraction techniques. The structure contains three-dimensionally linked Mn(9) units of a chiral "paddle-wheel" type. Experimental IR and Raman spectra were analyzed in terms of fundamental vanadate and hydroxide vibrational modes. The magnetic properties were investigated, and the specific heat in applied fields was studied. The dominant magnetic interactions (Mn(2+), S = 5/2) are of antiferromagnetic origin, as indicated by a Curie-Weiss fit above 175 K with Θ ≈ -200 K. Canting of the spins on the geometrically frustrated triangle segment of the structural feature is considered to account for the ferrimagnetic type of long-range order at T(C) ≈ 18 K. We propose a model for the spin structure in the ordered regime. Dielectric constants were measured and indicate a magnetodielectric effect at T(C), which is assigned to spin-lattice coupling.

Dimanganese(II) hydroxide vanadate, Mn2(OH)[VO4].

Dimanganese(II) hydroxide vanadate was obtained from hydro-thermal reactions. The crystal structure of the title compound is isotypic with that of Zn2(OH)[VO4]. Three crystallographically independent Mn(2+) ions are present, one (site symmetry .m.) with a distorted trigonal-bipyramidal and two (site symmetries .m. and 1) with distorted octa-hedral coordination spheres. These polyhedra are linked through common edges, forming a corrugated layer-type of structure extending parallel to (100). A three-dimensional framework results via additional Mn-O-V-O-Mn connectivities involving the two different tetra-hedral [VO4] units (each with point-group symmetry .m.). O-H⋯O hydrogen bonds (one bifurcated) between the OH functions (both with point-group symmetry .m.) and the [VO4] units complete this arrangement.

Crystal structure and magnetic properties of the S = 1/2 quantum spin system Cu7(TeO3)6F2 with mixed dimensionality.

The new oxofluoride Cu7(TeO3)6F2 has been synthesized by hydrothermal synthesis. It crystallizes in the triclinic system, space group P1. The crystal structure constitutes a Cu-O framework with channels extending along [001] where the F(-) ions and the stereochemically active lone-pairs on Te(4+) are located. From magnetic susceptibility, specific heat, and Raman scattering measurements we find evidence that the magnetic degrees of freedom of the Cu-O-Cu segments in Cu7(TeO3)6F2 lead to a mixed dimensionality with single Cu S = (1)/2 moments weakly coupled to spin-chain fragments. Due to the weaker coupling of the single moments, strong fluctuations exist at elevated temperatures, and long-range magnetic ordering evolves at comparably low temperatures (TN = 15 K).

Mild hydrothermal crystal growth, structure, and magnetic properties of ternary U(IV) containing fluorides: LiUF5, KU2F9, K7U6F31, RbUF5, RbU2F9, and RbU3F13.

Single crystals of several ternary alkali uranium fluorides, LiUF5, KU2F9, K7U6F31, RbUF5, RbU2F9, and RbU3F13, have been obtained in a mild hydrothermal process using UO2(CH3CO2)2(H2O)2 as the uranium source. Their crystal structures were determined by single crystal X-ray diffraction. The uranium in the starting reagent was successfully reduced from U(6+) to U(4+) in a dilute hydrofluoric acid environment, aided by the presence of a copper salt. All materials exhibit highly complex crystal structures that range from two-dimensional to three-dimensional. The U(4+) cations are found in high (UF8 and UF9) coordination environments. The magnetic susceptibility measurements yielded effective magnetic moments of 3.01-3.83 µB for the U(4+) cations. The temperature dependent magnetic susceptibility measurements confirmed that the U(4+) cation exhibits a nonmagnetic singlet ground state at low temperatures. No long-range magnetic order was observed for any of the above compositions down to 2 K. Optical and thermal behaviors of the fluorides were also investigated.

AAg2(M'(1/3)M(2/3))[VO4]2: synthesis, magnetic properties, and lattice dynamics of honeycomb-type lattices.

The magnetic honeycomb lattice series of compounds, AAg2(M'1/3M2/3)[VO4]2 with A = Ba(2+), Sr(2+), M' = Mg(2+), Zn(2+), and M = Mn(2+), Co(2+), and Ni(2+), have been synthesized and their physical properties are reported. This series of compounds contains the M' and M cations in a 1:2 ratio on a single crystallographic site. In an ordered arrangement, this could generate a magnetic honeycomb-type lattice. Presented X-ray diffraction data, spectroscopic measurements of lattice dynamics, along with ab initio calculations, magnetic, and specific heat data for these compounds clearly point toward the formation of magnetic honeycomb-type lattices.

Application of a mild hydrothermal approach containing an in situ reduction step to the growth of single crystals of the quaternary U(IV)-containing fluorides Na4MU6F30 (M = Mn2+, Co2+, Ni2+, Cu2+, and Zn2+) crystal growth, structures, and magnetic properties.

A family of rare U(IV)-containing quaternary fluorides, Na4MU6F30 (M = Mn(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)), was synthesized in single crystal form via a mild hydrothermal technique utilizing an in situ U(VI) to U(IV) reduction step. The modified hydrothermal route is described, and the conditions to obtain single crystals in high yield are detailed. The crystal structures were determined by single crystal X-ray diffraction. The isostructural fluorides crystallize in a new structure type in the trigonal space group P3̅c1. They exhibit a complex three-dimensional crystal structure consisting of corner- and edge-shared UF9 and MF6 polyhedra. The main building block, a U6F30(6-) group, is arranged to create two distinct hexagonal channels, inside which MF6 octahedra and Na(+) cations are located. The copper-containing member of the series, Na4CuU6F30, is unusual in that the Cu(2+) cation exhibits a rare symmetrical coordination environment consisting of six identical Cu-F bond distances, indicating the lack of the expected Jahn-Teller distortion. Magnetic susceptibility measurements of Na4ZnU6F30 yielded an effective magnetic moment of 3.42 µB for the U(4+) (f(2)) cation in the structure. Measurements of the other members containing magnetic transition-metal cations in addition to U(4+), Na4MU6F30 (M = Mn(2+), Co(2+), Ni(2+), and Cu(2+)) yielded total effective magnetic moments of 10.2, 9.84, 8.87, and 8.52 µB for the Mn-, Co-, Ni-, and Cu-containing materials, respectively. No evidence for long-range magnetic ordering was found down to 2 K. Measurements of the magnetization as a function of applied magnetic field at 2 K for Na4MnU6F30 confirmed that the U(4+) magnetic cation exhibits a nonmagnetic singlet ground state at low temperature. Thermal stability measurements and UV-vis diffuse reflectance spectroscopy are also reported.

Synthesis, crystal structures, magnetic, and thermal properties of divalent metal formate-formamide layered compounds.

A series of layered divalent metal formate compounds, [M(HCOO)2(HCONH2)2] (M = Mn (1Mn), Ni (2Ni), Cu(3Cu), Zn(4Zn), Mg(5Mg)), have been prepared by solvothermal synthesis and their room temperature (RT) and low-temperature (LT) crystal structures, and thermal and magnetic properties determined. All the compounds contain octahedral metal ions connected by four anti-anti formato ligands to form (4,4) nets with the composition of M(HCOO)2. The oxygen atoms from two coordinating formamide ligands above and below the layer complete the MO6 distorted octahedral coordination. Order-disorder phase transformations involving the formamide ligands were observed in the 1Mn, 2Ni, and 4Zn compounds. Like transitions in related formate structures with perovskite like topology, the transitions correspond to the ordering of the amine groups of the terminating formamide ligands which are disordered at ambient temperature. The magnetic properties of the three magnetic members of the series 1Mn, 2Ni, and 3Cu were investigated using microcrystalline samples, over the temperature range of 2 K-300 K under different applied fields. All compounds belong to antiferromagnetic square lattices with S = 5/2, 1, and 1/2. Exchange constants for a nearest neighbor model are presented here. Specific heat measurements indicate magnetic long-range order at lower temperatures, S = 5/2 (antiferromagnetic) and S = 1 (ferrimagnetic).

Ba(1-x)Na(x)Ti2Sb2O (0.0 ≤ x ≤ 0.33): a layered titanium-based pnictide oxide superconductor.

A new layered Ti-based pnictide oxide superconductor, Ba(1-x)Na(x)Ti(2)Sb(2)O (0.0 ≤ x ≤ 0.33), is reported. X-ray studies revealed that it crystallizes in the tetragonal CeCr(2)Si(2)C structure. The undoped parent compound, BaTi(2)Sb(2)O [P4/mmm; a = 4.1196(1) Å; c = 8.0951(2) Å], exhibits a charge density wave (CDW)/spin density wave (SDW) transition at 54 K. Upon chemical doping with Na, the CDW/SDW transition is systematically suppressed, and superconductivity arises with the critical temperature (T(c)) increasing to 5.5 K. Bulk superconductivity was confirmed by resistivity, magnetic, and heat capacity measurements. Like the high-T(c) cuprates and the iron pnictides, the superconductivity in BaTi(2)Sb(2)O arises from an ordered state. Similarities and differences between BaTi(2)Sb(2)O and the cuprate and iron pnictide superconductors are discussed.

Electronic excitations and lattice dynamics of coordinatively "unsaturated" complex transition metal compounds.

Single crystal polarized Raman and infrared spectra of the series Na(5)[MO(2)][X] with M = Co(I), Ni(I), and Cu(I) and X = S(2-) and CO(3)(2-), are reported. All phonon modes are assigned to the lattice eigenmodes based on the group theory analysis and first principles lattice dynamics calculations. The energies of the fundamental symmetric and asymmetric vibrations of the [MO(2)](3-) complex are discussed on the basis of their electronic structure and variation in M-O interatomic distances. Electronic Raman scattering and luminescence are observed for the magnetic members of the series (Co(I), d(8), and Ni(I), d(9)). Ligand field theory is employed to account for the electronic effects which originate from states split by spin-orbit coupling.

Synthesis, crystal structure, and physical properties of BaAg2Cu[VO4]2: a new member of the S = 1/2 triangular lattice.

By application of flux growth methods in combination with redox reactions, single crystals of BaAg(2)Cu[VO(4)](2) can be synthesized. A new structure type (triclinic, P1, Z = 2, a = 5.448(2) Å, b = 5.632(3) Å, c = 14.393(6) Å, α = 94.038(9)°, ß = 90.347(6)°, and γ = 118.195(5)°) has been found and will be described here. Structure-properties relationships have been investigated by spectroscopic methods (IR, UV-vis-NIR, ESR) and the electronic structure will be discussed within the angular-overlap model (AOM) for Cu(2+). Furthermore, we present the magnetization and specific heat data for BaAg(2)Cu[VO(4)](2) representing a Heisenberg spin system with exclusive super-super exchange (SSE) on a frustrated magnetic triangular lattice. Considerable antiferromagnetic (AFM) low-dimensional interaction is evident, and ferromagnetic-like long-range order sets in at ≈0.7 K.

Exposure of an adult population to perfluorinated substances using duplicate diet portions and biomonitoring data.

Because dietary intake is supposed to be an important route of human exposure we quantified the dietary intake of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHxS), perfluorohexanoate (PFHxA), and perfluorooctane sulfonamide (PFOSA) using 214 duplicate diet samples. The study was carried out with a study population of 15 female and 16 male healthy subjects aged 16-45 years. The participants collected daily duplicate diet samples over seven consecutive days in 2005. Duplicate samples were homogenized and their ultrasonic extracts were cleaned up by SPE and subjected to HPLC-ESI-MS/MS. In addition, individual intakes were estimated based on blood levels of PFOS and PFOA using a pharmacokinetic model. Blood samples were collected once during the sampling period. The median (90th percentile) daily dietary intake of PFOS and PFOA was 1.4 ng/kg b.w. (3.8 ng/kg b.w.) and 2.9 ng/kg b.w. (8.4 ng/kg b.w.), respectively. PFHxS and PFHxA could be detected only in some samples above detection limit with median (maximum) daily intakes of 2.0 ng/kg b.w. (4.0 ng/kg b.w.) and 4.3 ng/kg b.w. (9.2 ng/kg b.w.), respectively. Because PFOSA could not be detected above the limit of detection of 0.2 ng/g f.w. this indirect route of exposure seems to be of less significance. Overall, the results of this study demonstrate that the German population is exposed to PFOS and PFOA, but the median dietary intake did not reach the recommended tolerable daily intake by far. Biomonitoring data predict an exposure in a comparable range. We suppose that, normally, food intake is the main source of exposure of the general population to PFOS and PFOA.

Preparation, characterization, and magnetic behavior of the ln derivatives (ln = nd, la) of a 2,6-diiminepyridine ligand and corresponding dianion.

An unprecedented Nd[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N=C(CH(3))](2)(C(5)H(3)N)]NdI(2)(THF) (1) complex was prepared by oxidizing metallic Nd with I(2) in THF and in the presence of 2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N=C(CH(3))](2)(C(5)H(3)N). The magnetic behavior at variable T clearly indicated that the complex should be regarded as a trivalent Nd atom antiferromagnetically coupled to a radical anion. By using the doubly deprotonated form of the diimino pyridine ligand [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)](2-) (2) the corresponding trivalent complexes [[2,6-[[2,6-(i-Pr)(2)C(6)H(5)]N-C=CH(2)](2)(C(5)H(3)N)]Ln (THF)](mu-Cl)(2)[Li(THF)(2)].0.5 (hexane) [Ln = Nd (3), La (4)] were obtained and characterized. Reduction of these species afforded electron transfer to the ligand system which gave ligand dimerization via C-C bond formation through one of the two ene-amido functions of each molecule. The resulting dinuclear [[([2,6-(i-Pr)(2)C(6)H(5)]N-C=(CH(2)))(C(5)H(3)N)([2,6-(i-Pr)(2)C(6)H(5)]N=CCH(2))]Ln(THF)(2)(mu-Cl)[Li(THF)(3)])(2).2(THF) [Ln = Nd (5), La (6)] were isolated and characterized.