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Solid-gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF 3 ) 3 Pz]Ag} 3 and {[4-Br-3,5-(CF 3 ) 2 Pz]Ag} 3 supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF 3 ) 2 Pz]Ag} 3 under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above. Complete structural data of three novel silver-ethylene complexes are presented together with a thorough computational analysis of the mechanism., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A Mn(II) salt and A + CN - under anaerobic conditions react to form 2-D and 3-D extended structured compounds of A m Mn II n (CN) m+2n stoichiometry. Here, the creation and characterization of this large family of compounds, for example AMn II 3 (CN) 7 , A 2 Mn II 3 (CN) 8 , A 2 Mn II 5 (CN) 12 , A 3 Mn II 5 (CN) 13 , and A 2 Mn II [Mn II (CN) 6 ], where A represents alkali and tetraalkylammonium cations, is reviewed. Cs 2 Mn II [Mn II (CN) 6 ] has the typical Prussian blue face centered cubic unit cell. However, the other alkali salts are monoclinic or rhombohedral. This is in accord with smaller alkali cation radii creating void space that is minimized by increasing the van der Waals stabilization energy by reducing ∠Mn-N≡C, which, strengthens the magnetic coupling and increases the magnetic ordering temperatures. This is attributed to the non-rigidity of the framework structure due the significant ionic character associated with the high-spin Mn II sites. For larger tetraalkylammonium cations, the high-spin Mn sites lack sufficient electrostatic A + ⋅⋅⋅NC stabilization and form unexpected 4- and 5-coordinated Mn sites within a flexible, extended framework around the cation; hence, the size, shape, and charge of the cation dictate the unprecedented stoichio-metry and unpredictable cation adaptive structures. Antiferromagnetic coupling between adjacent Mn II sites leads to ferrimagnetic ordering, but in some cases antiferromagnetic coupling of ferrimagnetic layers are compensated and synthetic antiferromagnets are observed. The magnetic ordering temperatures for ferrimagnetic A 2 Mn II [Mn II (CN) 6 ] with both octahedral high- and low-spin Mn II sites increase with decreasing ∠Mn-N≡C. The crystal structures for all of the extended structured materials were obtained by powder diffraction., (© 2023 Wiley-VCH GmbH.)

Purification of C 2 H 4 from an C 2 H 4 /C 2 H 6 mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF 3 ) 2 Bp]Cu} 3 has features very desirable in an olefin-paraffin separation material. It binds ethylene exclusively over ethane generating [(CF 3 ) 2 Bp]Cu(C 2 H 4 ). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C 2 H 4 /C 2 H 6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a "live" picture of the reversible conversion between [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) and the ethylene-free sorbent in the solid-state, driven by the presence or removal of C 2 H 4 . Molecular structures of trinuclear {[(CF 3 ) 2 Bp]Cu} 3 and mononuclear [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) are also presented., (© 2021 Wiley-VCH GmbH.)

To identify the genesis of the differing magnetic behaviors for the ferro- (FO) and metamagnetic (MM) polymorphs of [FeCp* 2 ][TCNQ] (Cp* = pentamethylcyclopentadienide; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) the low temperature (18 ± 1 K) structures of each polymorph were determined from high-resolution synchrotron powder diffraction data. Each polymorph possesses chains of alternating S = 1/2 [FeCp* 2 ]˙ + cations and S = 1/2 [TCNQ]˙ + , but with differing relative orientations. These as well as an additional paramagnetic polymorph do not thermally interconvert. In addition, the room and low (<70 ± 10 K) temperature structures of the MM polymorph, MM RT and MM LT , respectively, differ from that previously reported at 167 K (-106 °C) MM structure, and no evidence of either phase transition was previously noted even from the magnetic data. This transition temperature and enthalpy of this phase transition for MM RT ⇌MM was determined to be 226.5 ± 0.4 K (-46.7 ± 0.4 °C) and 0.68 ± 0.04 kJ mol -1 upon warming, respectively, from differential calorimetry studies (DSC). All three MM phases are triclinic (P1[combining macron]) with the room temperature phase having a doubled unit cell relative to the other two. The lower temperature phase transition involves a small rearrangement of the molecular ions and shift in lattice parameters. These three MM and FO polymorphs have been characterized and form extended 1-D chains with alternating S = 1/2 [FeCp* 2 ]˙ + cations, and S = 1/2 [TCNQ]˙ - anions, whereas the fifth, paramagnetic (P) polymorph possesses S = 0 π-[TCNQ] 2 2- dimers. At 18 ± 1 K the intrachain FeFe separations are 10.738(2) and 10.439(3) Å for the FO and MM LT polymorphs, respectively. The key structural differences between FO and MM LT at 18 ± 1 K are the 10% shorter interchain NN and the 2.8% shorter intrachain FeFe separation present for MM LT . Computational analysis of all nearest-neighbor spin couplings for the 18 K structures of FO and MM LT indicates that the intrachain [FeCp* 2 ]˙ + [TCNQ]˙ - spin couplings (H = -2S i ·S j ) are the strongest (4.95 and 6.5 cm -1 for FO and MM LT , respectively), as previously hypothesized, and are ferromagnetic due to their S = 1/2 spins residing in orthogonal orbitals. The change in relative [TCNQ]˙ - [TCNQ]˙ - orientations leads to a computed change from the ferromagnetic interaction (0.2 cm -1 ) for FO to an antiferromagnetic interaction (-0.1 cm -1 ) for MM LT in accord with its observed antiferromagnetic ground state. Hence, the magnetic ground state cannot be solely described by the dominant magnetic interactions.

The reactions of Mn II (O 2 CCH 3 ) 2 with NEt 3 Me + CN - and NEt 2 Me 2 + CN - form (NEt 3 Me) 2 Mn II 5 (CN) 12 (1) and (NEt 2 Me 2 ) 2 Mn II 5 (CN) 12 (2), respectively. Structure model-building and Rietveld refinement of high-resolution synchrotron powder diffraction data revealed a cubic [a=24.0093 Å (1), 23.8804 Å (2)] 3D extended structural motif with adjacent tetrahedral and octahedral Mn II sites in a 3:2 ratio. Each tetrahedral Mn II site is surrounded by four low-spin octahedral Mn II sites, and each octahedral Mn II site is surrounded by six high-spin tetrahedral Mn II sites; adjacent sites are antiferromagnetically coupled in 3D. Compensation does not occur, and magnetic ordering as a ferrimagnet is observed at T c =13 K for 2 based on the temperature at which remnant magnetization, M r (T)→0. The hysteresis has an unusual constricted shape with inflection points around 50 and 1.2 kOe with a 5 K coercivity of 16 Oe and remnant magnetization, M r , of 2050 emuOe mol -1 . The unusual structure and stoichiometry are attributed to the very ionic nature of the high-spin N-bonded Mn II ion, which enables the maximization of the attractive van der Waals interactions through minimization of void space via a reduced ∠ MnNC. This results in an additional example of the A x Mn II y (CN) x+2y (x=0, y=1; x=1, y=3; x=2, y=1; x=2, y=2; x=2, y=3; x=3, y=5; and x=4, y=1) family of compounds possessing an unprecedented stoichiometry and lattice motif that are cation adaptive structured materials., (© 2020 Wiley-VCH GmbH.)

Understanding the electric dipole switching in multiferroic materials requires deep insight of the atomic-scale local structure evolution to reveal the ferroelectric mechanism, which remains unclear and lacks a solid experimental indicator in high-pressure prepared LiNbO 3 -type polar magnets. Here, we report the discovery of Zn-ion splitting in LiNbO 3 -type Zn 2 FeNbO 6 established by multiple diffraction techniques. The coexistence of a high-temperature paraelectric-like phase in the polar Zn 2 FeNbO 6 lattice motivated us to revisit other high-pressure prepared LiNbO 3 -type A 2 BB'O 6 compounds. The A-site atomic splitting (∼1.0-1.2 Å between the split-atom pair) in B/B'-mixed Zn 2 FeTaO 6 and O/N-mixed ZnTaO 2 N is verified by both powder X-ray diffraction structural refinements and high angle annular dark field scanning transmission electron microscopy images, but is absent in single-B-site ZnSnO 3 . Theoretical calculations are in good agreement with experimental results and suggest that this kind of A-site splitting also exists in the B-site mixed Mn-analogues, Mn 2 FeMO 6 (M = Nb, Ta) and anion-mixed MnTaO 2 N, where the smaller A-site splitting (∼0.2 Å atomic displacement) is attributed to magnetic interactions and bonding between A and B cations. These findings reveal universal A-site splitting in LiNbO 3 -type structures with mixed multivalent B/B', or anionic sites, and the splitting-atomic displacement can be strongly suppressed by magnetic interactions and/or hybridization of valence bands between d electrons of the A- and B-site cations.

We report a new polymorph of acridine, C 13 H 9 N, denoted form IX, obtained as thin needles by slow evaporation of a toluene solution. The structure was solved and refined from powder X-ray data. The structures of five unsolvated forms were previously known, but this is only the second with one mol-ecule in the asymmetric unit. The melting point [differential scanning calorimetry (DSC) onset] and heat of fusion are 108.8 (3) °C and 19.2 (4) kJ mol -1 , respectively.

Treating deuterohemin, chloro(deuteroporphyrinato)iron(III), with a non-coordinating base in DMSO/methanol allows for the isolation of [(deuteroporphyrinato)iron(III)] 2 , deuterohematin anhydride (DHA), an analogue of malaria pigment, the natural product of heme detoxification by malaria. The structure of DHA obtained from this solvent system has been solved by X-ray powder diffraction analysis and displays many similarities, yet important structural differences, to malaria pigment. Most notably, a water molecule of solvation occupies a notch created by the propionate side chains and stabilizes a markedly bent propionate ligand coordinated with a long Fe-O bond, and a carboxylate cluster associated with water molecules is generated. Together, these features account for its increased solubility and more open structure, with an increased porphyrin-porphyrin separation. The IR spectroscopic signature associated with this structure also accounts for the strong IR band at 1587 cm -1 seen for many amorphous preparations of synthetic malaria pigment, and it is proposed that stabilizing these structures may be a new objective for antimalarial drugs. The important role of the vinyl substituents in this biochemistry is further demonstrated by the structure of deuterohemin obtained by single-crystal X-ray diffraction analysis., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The reaction of Mn II (O 2 CMe) 2 and NaCN or LiCN in water forms a light green insoluble material. Structural solution and Rietveld refinement of high-resolution synchrotron powder diffraction data for this unprecedented, complicated compound of previously unknown composition revealed a new alkali-free ordered structural motif with [Mn II 4 (μ 3 -OH) 4 ] 4+ cubes and octahedral [Mn II (CN) 6 ] 4- ions interconnected in 3D by Mn II -N≡C-Mn II linkages. The composition is {[Mn II (OH 2 ) 3 ][Mn II (OH 2 )] 3 }(μ 3 -OH) 4 ][Mn II (μ-CN) 2 (CN) 4 ]⋅H 2 O=[Mn II 4 (μ 3 -OH) 4 (OH 2 ) 6 ][Mn II (μ-CN) 2 (CN) 4 ]⋅H 2 O, which is further simplified to [Mn 4 (OH) 4 ][Mn(CN) 6 ](OH 2 ) 7 (1). 1 has four high-spin (S=5/2) Mn II sites that are antiferromagnetically coupled within the cube and are antiferromagnetically coupled to six low-spin (S=1/2) octahedral [Mn II (CN) 6 ] 4- ions. Above 40 K the magnetic susceptibility, χ(T), can be fitted to the Curie-Weiss expression, χ ∝(T-θ) -1 , with θ=-13.4 K, indicative of significant antiferromagnetic coupling and 1 orders as an antiferromagnet at T c =7.8 K., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The size of the organic cation dictates both the composition and the extended 3-D structure for hybrid organic/inorganic Prussian blue analogues (PBAs) of A a Mn II b (CN) a+2 b (A = cation) stoichiometry. Alkali PBAs are typically cubic with both MC 6 and M'N 6 octahedral coordination sites and the alkali cation content depends on the M and M' oxidation states. The reaction of Mn II (O 2 CCH 3 ) 2 and A + CN - (A = NMe 4 , NEtMe 3 ) forms a hydrated material of A 3 Mn II 5 (CN) 13 composition. A 3 Mn II 5 (CN) 13 forms a complex, 3-D extended structural motif with octahedral and rarely observed square pyramidal and trigonal bipyramidal Mn II sites with a single layer motif of three pentagonal and one triangular fused rings. A complex pattern of Mn II CN chains bridge the layers. (NMe 4 ) 3 Mn II 5 (CN) 13 possesses one low-spin octahedral and four high-spin pentacoordinate Mn II sites and orders as an antiferromagnet at 11 K due to the layers being bridged and antiferromagnetically coupled by the nonmagnetic cyanides. These are rare examples of intrinsic, chemically prepared and controlled artificial antiferromagnets and have the advantage of having controlled uniform spacing between the layers as they are not physically prepared via deposition methods. A 3 Mn 5 (CN) 13 (A = NMe 4 , NEtMe 3 ) along with [NEt 4 ] 2 Mn II 3 (CN) 8 , [NEt 4 ]Mn II 3 (CN) 7 , and Mn(CN) 2 form stoichiometrically related A a Mn II b (CN) a+2 b ( a = 0, b = 1; a = 2, b = 3; a = 1, b = 3; and a = 3, b = 5) series possessing unprecedented stoichiometries and lattice motifs. These unusual structures and stoichiometries are attributed to the very ionic nature of the high-spin N-bonded Mn II ion that enables the maximization of the attractive van der Waals interactions via minimization of void space via a reduced ∠MnNC. This A a Mn II b (CN) a+2 b family of compounds are referred to as being cation adaptive in which size and shape dictate both the stoichiometry and structure.

Double corundum-related polar magnets are promising materials for multiferroic and magnetoelectric applications in spintronics. However, their design and synthesis is a challenge, and magnetoelectric coupling has only been observed in Ni 3 TeO 6 among the known double corundum compounds to date. Here we address the high-pressure synthesis of a new polar and antiferromagnetic corundum derivative Mn 2 MnWO 6 , which adopts the Ni 3 TeO 6 -type structure with low temperature first-order field-induced metamagnetic phase transitions (T N  = 58 K) and high spontaneous polarization (~ 63.3 μC·cm -2 ). The magnetostriction-polarization coupling in Mn 2 MnWO 6 is evidenced by second harmonic generation effect, and corroborated by magnetic-field-dependent pyroresponse behavior, which together with the magnetic-field-dependent polarization and dielectric measurements, qualitatively indicate magnetoelectric coupling. Piezoresponse force microscopy imaging and spectroscopy studies on Mn 2 MnWO 6 show switchable polarization, which motivates further exploration on magnetoelectric effect in single crystal/thin film specimens.

A novel 6H-type hexagonal perovskite Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 was prepared at high pressure (6 GPa) and temperature (1773 K). Both transmission electron microscopy and synchrotron powder X-ray diffraction data demonstrate that Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 crystallizes in P6 3 /mmc with face-shared (Cr 0.97(1) Te 0.03(1) )O 6 octahedral pairs interconnected with TeO 6 octahedra via corner-sharing. Structure analysis shows a mixed Cr 2+ /Cr 3+ valence state with ∼10% Cr 2+ . The existence of Cr 2+ in Ba 3 (Cr 2+ 0.10(1) Cr 3+ 0.87(1) Te 6+ 0.03 ) 2 TeO 9 is further evidenced by X-ray absorption near-edge spectroscopy. Magnetic properties measurements show a paramagnetic response down to 4 K and a small glassy-state curvature at low temperature. In this work, the octahedral Cr 2+ O 6 component is stabilized in an oxide material for the first time; the expected Jahn-Teller distortion of high-spin (d 4 ) Cr 2+ is not found, which is attributed to the small proportion of Cr 2+ (∼10%) and the face-sharing arrangement of CrO 6 octahedral pairs, which structurally disfavor axial distortion.

New layered honeycomb tellurates, BiM(III)TeO 6 (M = Cr, Mn, Fe) were synthesized and characterized. BiM(III)TeO 6 (M = Cr, Fe) species crystallize in a trigonal space group, P3̅1c (No. 163), of edge-sharing M 3+ /Te 6+ O 6 octahedra, which form honeycomb-like double layers in the ab plane with Bi 3+ cations located between the layers. Interestingly, the structure of BiMnTeO 6 is similar to those of the Cr/Fe analogues, but with monoclinic space group, P2 1 /c (No. 14), attributed to the strong Jahn-Teller distortion of Mn 3+ cations. The crystal structure of BiM(III)TeO 6 is a superstructure of PbSb 2 O 6 -related materials (ABB'O 6 ). The Cr 3+ and Fe 3+ cations are ordered 80% and 90%, respectively, while the Mn 3+ ions are completely ordered on the B-site of the ABB'O 6 structure. BiCrTeO 6 shows a broad antiferromagnetic transition (AFM) at ∼17 K with a Weiss temperature (θ) of -59.85 K, while BiFeTeO 6 and BiMnTeO 6 show sharp AFM transitions at ∼11 K with θ of -27.56 K and at ∼9.5 K with θ of -17.57 K, respectively. These differences in the magnetic behavior are ascribed to the different concentration of magnetic nearest versus next-nearest neighbor interactions of magnetic cations due to the relative differences in the extent of M/Te ordering.

Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2 FeMoO6 at unparalleled low temperatures of 150-300 (o) C. The irreversible ionic motion at ambient pressure, as evidenced by real-time powder synchrotron X-ray and neutron diffraction, and second harmonic generation, leads to a transition from a Ni3 TeO6 -type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties. This work demonstrates a remarkable cationic rearrangement, with corresponding large changes in the physical properties in a bulk oxide at unprecedented low temperatures., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to ∼120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s(2) lone-pair electrons, together with a surprising off-centering of Mn(2+) (d(5)) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN ≈ 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near ∼150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.

The crystal structures of NiX2(pyz)2 (X = Cl (1), Br (2), I (3), and NCS (4)) were determined by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN4X2 units that are bridged by pyz ligands. The 2D layered motifs displayed by 1-4 are relevant to bifluoride-bridged [Ni(HF2)(pyz)2]EF6 (E = P, Sb), which also possess the same 2D layers. In contrast, terminal X ligands occupy axial positions in 1-4 and cause a staggered packing of adjacent layers. Long-range antiferromagnetic (AFM) order occurs below 1.5 (Cl), 1.9 (Br and NCS), and 2.5 K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and g factor of 2, 3, and 4 were measured by electron-spin resonance with no evidence for zero-field splitting (ZFS) being observed. The magnetism of 1-4 spans the spectrum from quasi-two-dimensional (2D) to three-dimensional (3D) antiferromagnetism. Nearly identical results and thermodynamic features were obtained for 2 and 4 as shown by pulsed-field magnetization, magnetic susceptibility, as well as their Néel temperatures. Magnetization curves for 2 and 4 calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. Compound 3 is characterized as a 3D AFM with the interlayer interaction (J⊥) being slightly stronger than the intralayer interaction along Ni-pyz-Ni segments (J(pyz)) within the two-dimensional [Ni(pyz)2](2+) square planes. Regardless of X, J(pyz) is similar for the four compounds and is roughly 1 K.

The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides-semiconductors for photocatalytic overall water splitting-is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. We utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases were discovered in the GaN-Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900 °C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000 °C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.

The first transition-metal-only double perovskite compound, Mn(2+) 2 Fe(3+) Re(5+) O6 , with 17 unpaired d electrons displays ferrimagnetic ordering up to 520 K and a giant positive magnetoresistance of up to 220 % at 5 K and 8 T. These properties result from the ferrimagnetically coupled Fe and Re sublattice and are affected by a two-to-one magnetic-structure transition of the Mn sublattice when a magnetic field is applied. Theoretical calculations indicate that the half-metallic state can be mainly attributed to the spin polarization of the Fe and Re sites., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Investigation of an additional resonance peak in the (19) F solid-state nuclear magnetic resonance (NMR) spectrum of AMG 853, a dual antagonist of DP and CRTH2 previously in clinical development for asthma, has led to the identification of two conformational isomers coexisting in the crystal lattice in a continuous composition range between 89.7%:10.3% and 96.5%:3.5%. These two isomers differ in the chloro-flurorophenyl moiety orientation-the aromatic ring is flipped by 180° in these two isomers. The level of the minor isomer is directly measured through integration of the two peaks in the (19) F solid-state NMR spectrum. The values obtained from the NMR data are in excellent agreement with the degree of disorder of the fluorine atom in the crystal structure, refined using both single-crystal and high-resolution powder X-ray diffraction data., (© 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.)

Mn(2+)2 Fe(2+)W(6+)O6 , a new polar magnetic phase, adopts the corundum-derived Ni3TeO6 -type structure with large spontaneous polarization (PS) of 67.8 μC cm(-2), complex antiferromagnetic order below ≈75 K, and field-induced first-order transition to a ferrimagnetic phase below ≈30 K. First-principles calculations predict a ferrimagnetic (udu) ground state, optimal switching path along the c-axis, and transition to a lower energy udu-udd magnetic double cell., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

CsTlCl(3) and CsTlF(3) perovskites have been theoretically predicted to be superconductors when properly hole-doped. Both compounds have been previously prepared as pure compounds: CsTlCl(3) in a tetragonal (I4/m) and a cubic (Fm3̅m) perovskite polymorph and CsTlF(3) as a cubic perovskite (Fm3̅m). In this work, substitution of Tl in CsTlCl(3) with Hg is reported, in an attempt to hole-dope the system and induce superconductivity. The whole series CsTl(1-x)HgxCl(3) (x = 0.0, 0.1, 0.2, 0.4, 0.6, and 0.8) was prepared. CsTl(0.9)Hg(0.1)Cl(3) is tetragonal as the more stable phase of CsTlCl(3). However, CsTl(0.8)Hg(0.2)Cl(3) is already cubic with the space group Fm3̅m and with two different positions for Tl(+) and Tl(3+). For x = 0.4 and 0.5, solid solutions could not be formed. For x ≥ 0.6, the samples are primitive cubic perovskites with one crystallographic position for Tl(+), Tl(3+), and Hg(2+). All of the samples formed are insulating, and there is no signature of superconductivity. X-ray absorption spectroscopy indicates that all of the samples have a mixed-valence state of Tl(+) and Tl(3+). Raman spectroscopy shows the presence of the active Tl-Cl-Tl stretching mode over the whole series and the intensity of the Tl-Cl-Hg mode increases with increasing Hg content. First-principle calculations confirmed that the phases are insulators in their ground state and that Hg is not a good dopant in the search for superconductivity in this system.

Using a controllable wet chemical approach, the polyol process, we developed a cobalt carbide nanomagnet consisting of an assembly of Co2C and Co3C nanoparticles as an alternative to rare earth permanent magnets (PMs). The thermodynamically stable mixed phase cobalt carbide nanoparticles are shown to be acicular in morphology. Their exchange-coupled magnetic interaction possessing high maximum energy product of 20.7 kJ m(-3) and room temperature coercivity (2.9 kOe) has been confirmed through vibrating sample magnetometer (VSM) and first order reversal curves (FORCs). These metastable carbide nanoparticles offer improved magnetic properties compared to their pure bulk form. An understanding of the formation mechanism, using in situ time-resolved X-ray spectroscopy (TR-XAS), and the correlation between phase contributions to the properties are described in detail. Our strategy presents a controllable route to preparing the cobalt carbide nanomagnets, which could be potentially useful in permanent magnet clean energy applications. Additionally, the in situ apparatus offers a promising way to directly explore the effects of reaction variables for high-temperature wet chemical reactions.

In order to realize significant benefits from the assembly of solid-state materials from molecular cluster superatomic building blocks, several criteria must be met. Reproducible syntheses must reliably produce macroscopic amounts of pure material; the cluster-assembled solids must show properties that are more than simply averages of those of the constituent subunits; and rational changes to the chemical structures of the subunits must result in predictable changes in the collective properties of the solid. In this report we show that we can meet these requirements. Using a combination of magnetometry and muon spin relaxation measurements, we demonstrate that crystallographically defined superatomic solids assembled from molecular nickel telluride clusters and fullerenes undergo a ferromagnetic phase transition at low temperatures. Moreover, we show that when we modify the constituent superatoms, the cooperative magnetic properties change in predictable ways.

Above-room-temperature polar magnets are of interest due to their practical applications in spintronics. Here we present a strategy to design high-temperature polar magnetic oxides in the corundum-derived A2BB'O6 family, exemplified by the non-centrosymmetric (R3) Ni3TeO6-type Mn(2+)2Fe(3+)Mo(5+)O6, which shows strong ferrimagnetic ordering with TC = 337 K and demonstrates structural polarization without any ions with (n-1)d(10)ns(0), d(0), or stereoactive lone-pair electrons. Density functional theory calculations confirm the experimental results and suggest that the energy of the magnetically ordered structure, based on the Ni3TeO6 prototype, is significantly lower than that of any related structure, and accounts for the spontaneous polarization (68 μC cm(-2)) and non-centrosymmetry confirmed directly by second harmonic generation. These results motivate new directions in the search for practical magnetoelectric/multiferroic materials., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The crystal structure, redox electrochemical stability, and reaction chemistry of 1,4-dicyanotetrazine (DCNT) has been experimentally characterized. These experimental results were rationalized by the results of theoretical calculations of the electronic structure, spin and charge distributions, electronic absorption spectra, and electron affinity and compared with the results for related the tetracyano electron acceptors tetracyanoethylene (TCNE), 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), and 2,3,5,6-tetracyanopyrazine (TCNP). DCNT is made from the dehydration of 1,2,4,5-tetrazine-3,6-dicarboxamide, and because of the unusual deep-magenta color of the dicarboxamide in the solid state, its hydrogen-bonded layered structure, electronic structure, and electronic absorption spectra were determined. The magenta color is attributed to its absorptions at 532 nm (18 800 cm(-1)), and this corresponds to normalized chromaticity coordinates of x = 0.42 and y = 0.31 in the pink/red/orange part of the 1931 CIE chromaticity diagram. In contrast with previous reports, DCNT exhibits an irreversible one-electron reduction at -0.09 V vs SCE (MeCN), and reduced forms of DCNT have yet to be isolated and characterized. In addition, the reactions of DCNT with V(CO)6, Fe(II)(C5Me5)2, and I(-) are discussed.

Structural investigations of a nonstoichiometric hydrate, AMG 222 tosylate, a DPP-IV inhibitor in clinical development for type II diabetes, were performed using a multitechnique approach. The moisture sorption isotherm is in good agreement with a simple Langmuir model, suggesting that the hydrate water is located in well-defined crystallographic sites, which become vacant during dehydration. Crystal structures of AMG 222 tosylate at ambient and dry conditions were determined from high-resolution X-ray diffraction using the direct space method. On the basis of these crystal structures, hydrated water is located in channels formed by the drug framework. Upon dehydration, an isostructural dehydrate is formed with the channels remaining void and accessible to water for rehydration. Kitaigorodskii packing coefficients of the solid between relative humidity of 0% and 90% indicate that the equilibrium form of AMG 222 tosylate is the fully hydrated monohydrate., (© 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.)

Polar oxides are technically of great interest but difficult to prepare. Our recent discoveries predicted that polar oxides can be synthesized in the corundum-derivative A2BB'O6 family with unusually small cations at the A-site and a d(0) electron configuration ion at B'-site. When magnetic transition-metal ions are incorporated more interesting polar magnetic oxides can form. In this work we experimentally verified this prediction and prepared LiNbO3 (LN)-type polar magnetic Zn2FeTaO6 via high pressure and temperature synthesis. The crystal structure analysis indicates highly distorted ZnO6 and (Fe/Ta)O6 octahedra, and an estimated spontaneous polarization (PS) of ∼50 μC/cm(2) along the c-axis was obtained from point charge model calculations. Zn2Fe(3+)Ta(5+)O6 has a lower magnetic transition temperature (TN ∼ 22 K) than the Mn2FeTaO6 analogue but is less conductive. The dielectric and polarization measurements indicate a potentially switchable component.

Li[TCNE] (TCNE = tetracyanoethylene) magnetically orders as a weak ferromagnet (canted antiferromagnet) below 21.0 ± 0.1 K, as observed from the bifurcation of the field-cooled and zero-field-cooled magnetizations, as well as remnant magnetization. The structure, determined ab initio from synchrotron X-ray powder diffraction data, consists of a planar μ4-[TCNE](•-) bound to four tetrahedral Li(+) ions. The structure consists of two interpenetrating diamondoid sublattices, with closest interlattice distances of 3.43 and 3.48 Å. At 5 K this magnetic state is characterized by a coercivity of ~30 Oe, a remnant magnetization of 10 emu·Oe/mol, and a canting angle of 0.5°.

The reaction of first row transition M(II) ions with KSCN in various solvents form tetrahedral (NMe4)2[M(II)(NCS)4] (M = Fe, Co), octahedral trans-M(II)(NCS)2(Sol)4 (M = Fe, V, Ni; Sol = MeCN, THF), and K4[M(II)(NCS)6] (M = V, Ni). The reaction of M(NCS)2(OCMe2)2 (M = Cr, Mn) in MeCN and [Co(NCMe)6](BF4)2 and KSCN in acetone and after diffusion of diethyl ether form M(NCS)2(Sol)2 that structurally differ as they form one-dimensional (1-D) (M = Co; Sol = THF), two-dimensional (2-D) (M = Mn; Sol = MeCN), and three-dimensional (3-D) (M = Cr; Sol = MeCN) extended structures. 1-D Co(NCS)2(THF)2 has trans-THFs, while the acetonitriles have a cis geometry for 2- and 3-D M(NCS)2(NCMe)2 (M = Cr, Mn). 2-D Mn(NCS)2(NCMe)2 is best described as Mn(II)(μ(N,N)-NCS)(μ(N,S)-NCS)(NCMe)2 [= Mn2(μ(N,N)-NCS)2(μ(N,S)-NCS)2(NCMe)4] with the latter μ(N,S)-NCS providing the 2-D connectivity. In addition, the reaction of Fe(NCS)2(OCMe2)2 and 7,7,8,8-tetracyanoquino-p-dimethane (TCNQ) forms 2-D structured Fe(II)(NCS)2TCNQ. The magnetic behavior of 1-D Co(NCS)2(THF)2 can be modeled by a 1-D Fisher expression (H = -2JS(i)·S(j)) with g = 2.4 and J/kB = 0.68 K (0.47 cm(-1)) and exhibit weak ferromagnetic coupling. Cr(NCS)2(NCMe)2 and Fe(II)(NCS)2TCNQ magnetically order as antiferromagnets with Tc's of 37 and 29 K, respectively, while Mn(NCS)2(NCMe)2 exhibits strong antiferromagnetic coupling. M(NCS)2(THF)4 and K4[M(NCS)6] (M = V, Ni) are paramagnets with weak coupling between the octahedral metal centers.

We describe a solid-state material formed from binary assembly of atomically precise molecular clusters. [Co6Se8(PEt3)6][C60]2 and [Cr6Te8(PEt3)6][C60]2 assembled into a superatomic relative of the cadmium iodide (CdI2) structure type. These solid-state materials showed activated electronic transport with activation energies of 100 to 150 millielectron volts. The more reducing cluster Ni9Te6(PEt3)8 transferred more charge to the fullerene and formed a rock-salt-related structure. In this material, the constituent clusters are able to interact electronically to produce a magnetically ordered phase at low temperature, akin to atoms in a solid-state compound.

The structural, spectroscopic and magnetic properties of the two-dimensional (2D) molecule-based magnets of [Mn(II)(TCNE)(NCMe)2]X (X = PF6, AsF6, SbF6; TCNE = tetracyanoethylene, NCMe = acetonitrile) composition are reported. It is shown that the alteration of the interlayer distance by increasing the anion size has little effect on the critical magnetic ordering temperature, Tc, suggesting that it depends predominantly on the intra-plane magnetic exchange. The observed field-induced irreversibility in static magnetization, a slow decay of isothermal remanence below Tc, and the dynamic susceptibility data are in accord with a re-entrant spin-glass nature of the ground state of all materials. In contrast to the isostructural Fe-based magnets, in which strong magnetocrystalline anisotropy facilitates the finite temperature magnetic ordering with the magnetization easy axis perpendicular to the μ4-TCNE(•-) plane, in the studied Mn-based magnets the easy axis is canted away from the normal direction, due to a small magnetocrystalline anisotropy. The two magnetic transitions observed on cooling are assigned to the ferrimagnetic long-range ordering of the normal magnetization component followed by the re-entrant spin-glass type transition resulting from a random freezing of the in-plane magnetization component.

A key property that drives research in ferroelectric perovskite oxides is their strong piezoelectric response in which an electric field is induced by an applied strain, and vice versa for the converse piezoelectric effect. We have achieved an experimental enhancement of the piezoelectric response and dielectric tunability in artificially layered epitaxial PbTiO(3)/CaTiO(3) superlattices through an engineered rotation of the polarization direction. As the relative layer thicknesses within the superlattice were changed from sample to sample we found evidence for polarization rotation in multiple x-ray diffraction measurements. Associated changes in functional properties were seen in electrical measurements and piezoforce microscopy. The results demonstrate a new approach to inducing polarization rotation under ambient conditions in an artificially layered thin film.

Linear chain thiocyanate complexes of M(NCS)(2)(OCMe(2))(2) (M = Fe, Mn, Cr) composition have been prepared and structurally, chemically, and magnetically characterized. Fe(NCS)(2)(OCMe(2))(2) exhibits metamagnetic-like behavior, and orders as an antiferromagnet at 6 K. The Mn and Cr compounds are antiferromagnets with T(c) of 30 and 50 K, respectively, with J/k(B) = -3.5 (-2.4 cm(-1)) and -9.9 K (-6.9 cm(-1)), respectively, when fit to one-dimensional (1-D) Fisher chain model (H = -2JS(i)·S(j)). Co(NCS)(2) was prepared by a new synthetic route, and powder diffraction was used to determine its structure to be a two-dimensional (2-D) layer with μ(N,S,S)-NCS motif, and it is an antiferromagnet (T(c) = 22 K; θ = -33 K for T > 25 K). M(NCS)(2)(OCMe(2))(2) (M = Fe, Mn) and Co(NCS)(2) react with (NBu(4))(TCNE) in dichloromethane to form M(TCNE)[C(4)(CN)(8)](1/2), and in acetone to form M[C(4)(CN)(8)](OCMe(2))(2) (M = Fe, Mn, Co). These materials possess μ(4)-[C(4)(CN)(8)](2-) that form 2-D layered structural motifs, which exhibit weak antiferromagnetic coupling. Co(TCNE)[C(4)(CN)(8)](1/2) behaves as a paramagnet with strong antiferromagnetic coupling (θ = -50 K).

Malaria pigment, the heme detoxification product of malaria's invasion, digestion, and growth inside mammalian red blood cells, is an insoluble phase of iron(III)protoporphyrin-IX. Even though its structure was determined in 2000 by powder X-ray diffraction, significant questions remain about its formation and possible interaction with quinoline antimalarial drugs. A recent structural study, also with X-ray powder diffraction, has reconfirmed that the material isolated from the parasite is isostructural with its synthetic equivalent. It was recently suggested that other isomers may also be formed and may be present in synthetic samples. In particular, a series of stereoisomers are possible for the arrangement of vinyl groups on the periphery of the dimerized porphyrin rings. In principle, any given dimer can have vinyl groups at the α or β sites, and at γ or δ sites. In this paper, several models are evaluated, both biphasic and homogeneous methyl/vinyl disorder, against several sets of diffraction data, both published and new. We conclude that methyl/vinyl disorder is intrinsic to the system, and that the evidence at hand does not support the existence of any other crystalline isomers in carefully prepared samples of either natural or synthetic samples. Finally, the porphyrin-porphyrin interactions are evaluated using Scheidt's indicies for porphyrin π-stacking, and we find modest to weak π-interactions in these condensed phases., (Copyright © 2012 Verlag Helvetica Chimica Acta AG, Zürich.)

A further example of using a covalent-bond-forming reaction to alter supramolecular assembly by modification of hydrogen-bonding possibilities is presented. This concept was introduced by Lemmerer, Bernstein & Kahlenberg [CrystEngComm (2011), 13, 55-59]. The title structure, C(9)H(11)N(3)O·C(7)H(6)O(4), which consists of a reacted niazid molecule, viz. N'-(propan-2-ylidene)nicotinohydrazide, and 2,4-dihydroxybenzoic acid, was solved from powder diffraction data using simulated annealing. The results further demonstrate the relevance and utility of powder diffraction as an analytical tool in the study of cocrystals and their hydrogen-bond interactions.

The reaction of Mn(II) and [NEt(4)]CN leads to the isolation of solvated [NEt(4)]Mn(3)(CN)(7) (1) and [NEt(4)](2) Mn(3)(CN)(8) (2), which have hexagonal unit cells [1: R3m, a = 8.0738(1), c = 29.086(1) Å; 2: P3m1, a = 7.9992(3), c = 14.014(1) Å] rather than the face centered cubic lattice that is typical of Prussian blue structured materials. The formula units of both 1 and 2 are composed of one low- and two high-spin Mn(II) ions. Each low-spin, octahedral [Mn(II)(CN)(6)](4-) bonds to six high-spin tetrahedral Mn(II) ions through the N atoms, and each of the tetrahedral Mn(II) ions are bound to three low-spin octahedral [Mn(II)(CN)(6)](4-) moieties. For 2, the fourth cyanide on the tetrahedral Mn(II) site is C bound and is terminal. In contrast, it is orientationally disordered and bridges two tetrahedral Mn(II) centers for 1 forming an extended 3D network structure. The layers of octahedra are separated by 14.01 Å (c axis) for 2, and 9.70 Å (c/3) for 1. The [NEt(4)](+) cations and solvent are disordered and reside between the layers. Both 1 and 2 possess antiferromagnetic superexchange coupling between each low-spin (S = 1/2) octahedral Mn(II) site and two high-spin (S = 5/2) tetrahedral Mn(II) sites within a layer. Analogue 2 orders as a ferrimagnet at 27(±1) K with a coercive field and remanent magnetization of 1140 Oe and 22,800 emuOe mol(-1), respectively, and the magnetization approaches saturation of 49,800 emuOe mol(-1) at 90,000 Oe. In contrast, the bonding via bridging cyanides between the ferrimagnetic layers leads to antiferromagnetic coupling, and 3D structured 1 has a different magnetic behavior to 2. Thus, 1 is a Prussian blue analogue with an antiferromagnetic ground state [T(c) = 27 K from d(χT)/dT]., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A tetragonal polymorph of [Ni(HF(2))(pyz)(2)]PF(6) (designated β) is isomorphic to its SbF(6)-congener at 295 K and features linear Ni-FHF-Ni pillars. Enhancements in the spin exchange (J(FHF) = 7.7 K), Néel temperature (T(N) = 7 K), and critical field (B(c) = 24 T) were found relative to monoclinic α-PF(6). DFT reveals that the HF(2)(-) bridges are significantly better mediators of magnetic exchange than pyz (J(pyz)), where J(FHF) ≈ 3J(pyz), thus leading to quasi-1D behavior. Spin density resides on all atoms of the HF(2)(-) bridge whereas N-donor atoms of the pyz ring bear most of the density.

The mechanism of Ni substitution into the oxide semiconductor InTaO(4) has been studied through a combination of structural and spectroscopic techniques, providing insights into its previously reported photoactivity. Magnetic susceptibility and X-ray absorption near-edge spectroscopy (XANES) measurements demonstrate that nickel is divalent within the host lattice. The combined refinement of synchrotron X-ray and neutron powder diffraction data indicates that the product of Ni doping has the stoichiometry of (In(1-x)Ni(2x/3)Ta(x/3))TaO(4) with a solubility limit of x ≈ 0.18, corresponding to 12% Ni on the In site. Single-phase samples were only obtained at synthesis temperatures of 1150 °C or higher due to the sluggish reaction mechanism that is hypothesized to result from small free energy differences between (In(1-x)Ni(2x/3)Ta(x/3))TaO(4) compounds with different x values. Undoped InTaO(4) is shown to have an indirect band gap of 3.96 eV, with direct optical transitions becoming allowed at photon energies in excess of 5.1 eV. Very small band-gap reductions (less than 0.2 eV) result from Ni doping, and the origin of the yellow color of (In(1-x)Ni(2x/3)Ta(x/3))TaO(4) compounds instead results from a weak (3)A(2g) → (3)T(1g) internal d → d transition not associated with the conduction or valence band that is common to oxide compounds with Ni(2+) in an octahedral environment.

One striking anomaly of water ice has been largely neglected and never explained. Replacing hydrogen (1H) by deuterium (2H) causes ice to expand, whereas the normal isotope effect is volume contraction with increased mass. Furthermore, the anomaly increases with temperature T, even though a normal isotope shift should decrease with T and vanish when T is high enough to use classical nuclear motions. In this study, we show that these effects are very well described by ab initio density-functional theory. Our theoretical modeling explains these anomalies, and allows us to predict and to experimentally confirm a counter effect, namely, that replacement of 16O by 18O causes a normal lattice contraction.

Grinding of a one-dimensional (1-D) ladder coordination polymer (CP), [Zn(μ-CH(3)CO(2))(CF(3)CO(2))bpe] (1), and a hydrogen-bonded 1-D CP, [Cd(CH(3)CO(2))(2)bpe(H(2)O)] (2), with KBr resulted in the exchange of carboxylate by bromide ions and the formation of 1-D zigzag and 2-D CPs respectively., (This journal is © The Royal Society of Chemistry 2012)

Thermolysis of either the 3-D, bridged-layered [NEt(4)]Mn(II)(3)(CN)(7) or 2-D, layered [NEt(4)](2)Mn(II)(3)(CN)(8) forms Mn(II)(CN)(2). Rietveld analysis of the high-resolution synchrotron powder X-ray diffraction data determined that Mn(II)(CN)(2) is cubic [a = 6.1488(3) Å] (space group = Pn3m) consisting of two independent, interpenetrating networks having the topology of the diamond lattice. Each tetrahedrally coordinated Mn(II) is bonded to four orientationally disordered cyanide ligands. Mn(II)(CN)(2) magnetically orders as an antiferromagnet with a T(c) = 73 K determined from the peak in d(χT)/dT. Exchange coupling estimated via the mean field Heisenberg model from the transition temperature (J/k(B) = -4.4 K) and low temperature magnetic susceptibility of the ordered phase (J/k(B) = -7.2 K) indicate that Mn(II)(CN)(2) experiences weak antiferromagnetic coupling. The discrepancy between those estimates is presumably due to local anisotropy at the Mn(II) sites arising from the CN orientational disorder or interactions between the interpenetrating lattices.

Square-planar S = 1/2 Ag(II) ions in polymeric Ag(nic)(2) are linked by bridging nic monoanions to yield 2D corrugated sheets. Long-range magnetic order occurs below T(N) = 11.8(2) K due to interlayer couplings that are estimated to be about 30 times weaker than the intralayer exchange interaction.

The aqueous reaction of Mn(II) and NaCN leads to the isolation of the 3-D Prussian blue analogue (PBA) Na(2)Mn[Mn(CN)(6)]·2H(2)O (1·H(2)O), which under careful dehydration forms 1. 1·H(2)O is monoclinic [P2(1)/n, a = 10.66744(32) Å, b = 7.60223(23) Å, c = 7.40713(22) Å, β = 92.4379(28)°], while 1 is rhombohedral [R ̅3, a = 6.6166(2) Å, c = 19.2585(6) Å], and both structures are atypical for PBAs, which are typically face centered cubic. Most notably, the average ∠Mn-N-C angles are 165.3(3)° and 142.4(4)° for 1·H(2)O and 1, respectively, which are significantly reduced from linearity. This is attributed to the ionic nature of high-spin Mn(II) accommodating a reduced ∠Mn-N-C to minimize void space. Both 1 and 1·H(2)O magnetically order as ferrimagnets below their ordering temperature, T(c), of 58 and 30 K, respectively, as determined from the average of several independent methods. 1 and 1·H(2)O are hard magnets with 5 K coercive fields of 15,300 and 850 Oe, and remnant magnetizations of 9075 and 102 emu·Oe/mol, respectively. These data along with previous T(c)'s reported for related materials reveal that T(c) increases as the ∠Mn-N-C deviates further from linearity. Hence, the bent cyanide bridges play a crucial role in the superexchange mechanism by increasing the coupling via shorter Mn(II)···Mn(II) separations, and perhaps an enhanced overlap., (© 2011 American Chemical Society)

The reaction of Hg(OAc)(2) with 1,4-benzenedithiol in ethylenediamine at 80 °C yields [Hg(SC(6)H(4)S)(en)](n), while the reaction of Pb(OAc)(2) with 1,4-benzenedithiol in diethylenetriamine at 130 °C yields [Pb(SC(6)H(4)S)(dien)](n). Both products are crystalline materials, and structure determination by synchrotron X-ray powder diffraction revealed that both are essentially one-dimensional metal-organic polymers with -M-SC(6)H(4)S- repeat units. Diffuse reflectance UV-visible spectroscopy indicates band gaps of 2.89 eV for [Hg(SC(6)H(4)S)(en)](n) and 2.54 eV for [Pb(SC(6)H(4)S)(dien)](n), while density functional theory (DFT) band structure calculations yielded band gaps of 2.24 and 2.10 eV, respectively. The two compounds are both infinite polymers of metal atoms linked by 1,4-benzenedithiolate, the prototypical molecule for single-molecule conductivity studies, yet neither compound has significant electrical conductivity as a pressed pellet. In the case of [Pb(SC(6)H(4)S)(dien)](n) calculations indicate fairly flat bands and therefore low carrier mobilities, while the conduction band of [Hg(SC(6)H(4)S)(en)](n) does have moderate dispersion and a calculated electron effective mass of 0.29·m(e). Hybridization of the empty Hg 6s orbital with SC(6)H(4)S orbitals in the conduction band leads to the band dispersion, and suggests that similar hybrid materials with smaller band gaps will be good semiconductors.

Cu(5)SbO(6) is found to have a monoclinic, Delafossite-derived structure consisting of alternating layers of O-Cu(I)-O sticks and magnetic layers of Jahn-Teller distorted Cu(II)O(6) octahedra in an edge sharing honeycomb arrangement with Sb(V)O(6) octahedra. This yields the structural formula Cu(I)(3)Cu(II)(2)Sb(V)O(6). Variants with ordered and disordered layer stacking are observed, depending on the synthesis conditions. The spin ½ Cu(2+) ions form dimers in the honeycomb layer. The magnetic susceptibility measured between 5 and 300 K is characteristic of the presence of a singlet-triplet spin gap of 189 K. High resolution synchrotron X-ray diffraction studies indicate that changes in the intra- or interdimer distances between 300 and 20 K, such as might indicate an increase in strength of the Peierls-like distortion through the spin gap temperature, if present, are very small. A comparison to the NaFeO(2)-type Cu(2+) honeycomb compounds Na(3)Cu(2)SbO(6) and Na(2)Cu(2)TeO(6) is presented.

A co-crystal of two polymorphic active pharmaceutical ingredients (APIs), first reported and patented in 1937, has been prepared and thoroughly characterised, including crystal structure analysis. The existence of four crystal forms of one of the APIs, the sedative and hypnotic active pharmaceutical ingredient 3,3-diethyl-2,4(1H,3H)-pyridinedione, pyrithyldione (PYR), and of three crystal forms of the co-crystal-forming second API, the non-steroidal anti-inflammatory drug 1,2-dihydro-1,5-dimethyl-4-(1-methylethyl)-2-phenyl-3H-pyrazol-3-one, propyphenazone (PROP), has been reported previously, but they have only been partly characterised. For both compounds, none of the metastable forms exist at room temperature. DSC, hot-stage microscopy, X-ray diffraction and powder synchrotron X-ray diffraction were employed to characterise the polymorphic forms and to determine the crystal structures of forms I-III of PYR and forms I and II of PROP., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The crystal structures of the isostructural title compounds poly[(μ-benzene-1,4-dithiolato)dithallium], Tl(2)(SC(6)H(4)S), and poly[(μ-benzene-1,4-diselenolato)dithallium], Tl(2)(SeC(6)H(4)Se), were solved by simulated annealing from high-resolution synchrotron X-ray powder diffraction. Rietveld refinements of an initial structure with one formula unit per triclinic cell gave satisfactory agreement with the data, but led to a structure with impossibly close non-bonded contacts. A disordered model was proposed to alleviate this problem, but an alternative supercell structure leads to slightly improved agreement with the data. The isostructural superlattice structures were confirmed for both compounds through additional data collection, with substantially better counting statistics, which revealed the presence of very weak superlattice peaks not previously seen. Overall, each structure contains Tl-S or Tl-Se two-dimensional networks, connected by phenylene bridges. The sulfur (or selenium) coordination sphere around each thallium is a highly distorted square pyramid or a 'see-saw' shape, depending upon how many Tl-S or Tl-Se interactions are considered to be bonds. In addition, the two compounds contain pairs of Tl(I) ions that interact through a closed-shell 'thallophilic' interaction: in the sulfur compound there are two inequivalent pairs of Tl atoms with Tl-Tl distances of 3.49 and 3.58 Å, while in the selenium compound those Tl-Tl interactions are at 3.54 and 3.63 Å.