Structural trends from a consistent set of single-crystal data of REFeAsO (RE = La, Ce, Pr, Nd, Sm, Gd, and Tb)

A new crystal growth technique for single-crystals of REFeAsO (RE = La, Ce, Pr, Nd, Sm, Gd, and Tb) using NaI/KI as flux is presented. Crystals with a size up to 300 $\mu$m were isolated for single-crystal X-ray diffraction measurements. Lattice parameters were determined by LeBail fits of X-ray powder data against LaB6 standard. A consistent set of structural data is obtained and interpreted in a hard-sphere model. Effective radii for the rare-earth metal atoms for REFeAsO are deduced. The relation of the intra- and inter-plane distances of the arsenic atoms is identified as limiter of the phase formation, and its influence on Tc is discussed.Comment: 8 pages, 11 figures, 3 tables, fig. 6 changed to numerical plot, minor changes to the text, accepted for publication in PR

Anisotropic electrical resistivity of LaFeAsO: evidence for electronic nematicity

Single crystals of LaFeAsO were successfully grown out of KI flux. Temperature dependent electrical resistivity was measured with current flow along the basal plane, \rho_perpend(T), as well as with current flow along the crystallographic c-axis, \rho_parallel(T), the latter one utilizing electron beam lithography and argon ion beam milling. The anisotropy ratio was found to lie between \rho_parallel/\rho_perpend = 20 - 200. The measurement of \rho_perpend(T) was performed with current flow along the tetragonal [1 0 0] direction and along the [1 1 0] direction and revealed a clear in-plane anisotropy already at T \leq 175 K. This is significantly above the orthorhombic distortion at T_0 = 147 K and indicates the formation of an electron nematic phase. Magnetic susceptibility and electrical resistivity give evidence for a change of the magnetic structure of the iron atoms from antiferromagnetic to ferromagnetic arrangement along the c-axis at T^\ast = 11 K.Comment: 10 pages, 6 figures, minor change

Syntheses, crystal structure and magnetic properties of Tl9RETe6 (RE = Ce, Sm, Gd)

The three compounds Tl9RETe6 with RE = Ce, Sm, Gd were synthesized from the elements at 1020 K. Their isostructural crystal structures are ordered derivatives of the Tl5Te3 type with rare-earth metal and thallium occupying different Wyckoff positions. The structures can be understood as charge-ordered in accordance with the Zintl-Klemm concept: 9 Tl+ + RE3+ + 6 Te2-. DFT calculations for Tl9GdTe6, however, result in a low, but finite density of states at the Fermi level. Magnetic data confirm trivalent Gd, but indicate a small amount of Ce4+ in Tl9CeTe6; no indications for long-range magnetic order was found down to T = 2 K

Magnetic behavior of EuCu2As2: Delicate balance between antiferromagnetic and ferromagnetic order

The Eu-based compound, EuCu2As2, crystallizing in the ThCr2Si2-type tetragonal structure, has been synthesized and its magnetic behavior has been investigated by magnetization (M), heat-capacity (C) and electrical resistivity (rho) measurements as a function of temperature (T) and magnetic field (H) as well as by 151Eu Moessbauer measurements. The results reveal that Eu is divalent ordering antiferromagnetically below 15 K in the absence of magnetic field, apparently with the formation of magnetic Brillouin-zone boundary gaps. A fascinating observation is made in a narrow temperature range before antiferromagnetism sets in: That is, there is a remarkable upturn just below 20 K in the plot of magnetic susceptibility versus T even at low fields, as though the compound actually tends to order ferromagnetically. There are corresponding anomalies in the magnetocaloric effect data as well. In addition, a small application of magnetic field (around 1 kOe at 1.8 K) in the antiferromagnetic state causes spin-reorientation effect. These results suggest that there is a close balance between antiferromagnetism and ferromagnetism in this compoundComment: Phys. Rev. B, in pres

Anion-driven tetrel bond-induced engineering of lead(II) architectures with N′-(1-(2-pyridyl)ethylidene)nicotinohydrazide : experimental and theoretical findings

The evaluation of N′-(1-(2-pyridyl)ethylidene)nicotinohydrazide (HL) as a linker for the PbII tagged extended structures is described. The reaction of Pb(ClO4)2 or Pb(OAc)2 with HL in MeOH at 60 °C and room temperature, respectively, leads to heteroleptic complexes {[PbL]ClO4}n·nH2O and [PbL(OAc)]2, while the same reaction of Pb(ClO4)2 with HL at 60 °C in the presence of two equivalents of NaOAc or NaNO2 leads to heteroleptic complexes {[Pb(HL)(OAc)]ClO4}n and [PbL(NO2)]n, respectively. Using Pb(NO3)2 as a source of PbII in the same reaction with HL and two equivalents of NaN3 or NaNCS at room temperature yields [PbLN3]n and [Pb2(HL)2(NO3)2(NCS)2], respectively. The room temperature reaction of Pb(NO3)2 with HL in the presence of two equivalents of NaClO4 leads to the transformation of the parent ligand to its perchlorate salt [H2L]ClO4. In all the obtained PbII structures, HL or its deprotonated form L acts both as a chelating and a bridging ligand. The nature of the inorganic anion also influences the final structure. In all complexes the PbII center exhibits a hemidirected coordination geometry with all the covalent bonds being concentrated on one hemisphere of the coordination sphere with the closest approach of two atoms on the other side varying from 151° to 232°. The sterically available PbII ion participates in tetrel bonding as evidenced from the detailed structural analysis of the described complexes. As a result of tetrel bonding, the structures of all the six compounds can be extended to a higher dimensional framework, which is further stabilized by π⋯π stacking interactions between the aromatic rings. The DFT based charge and energy decomposition (ETS-NOCV) calculations are performed in order to shed light on the nature of non-covalent interactions that determine the stability of the obtained structures