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Ruddlesden–Popper oxides, (AO)(ABO3)n, occupy a prominent place in the landscape of materials research because of their intriguing potential applications. Compositional modifications to the cation sublattices, A or B, have been explored in order to achieve enhanced functionalities. However, changes to the anionic sublattice have been much less explored. In this work, new oxygen‐deficient manganese Ruddlesden–Popper‐related phases, La0.5Ca2.5Mn2O6.5 and La0.5Ca2.5Mn2O6.25, have been synthesized by controlled reduction of the fully oxidized n = 2 term La0.5Ca2.5Mn2O7. A complete structural and compositional characterization, by means of neutron diffraction, electron diffraction and atomically resolved scanning transmission electron microscopy and electron energy‐loss spectroscopy techniques, allows the proposition of a topotactic reduction pathway through preferential oxygen removal in the [MnO2] layers along [031] and [] directions. The gradual decrease of the Mn oxidation state, accommodated by short‐range ordering of anionic vacancies, reasonably explains the breaking of ferromagnetic interactions reinforcing the emergence of antiferromagnetic ones. Additional short‐range order–disorder phenomena of La and Ca cations have been detected in the reduced La0.5Ca2.5Mn2O7−δ, as previously reported in the parent compound. [ABSTRACT FROM AUTHOR]

The synthesis of a series of 4-aryl-3,5-bis(arylethynyl)aryl-4 H-1,2,4-triazoles derivatives is reported and the influence exerted by peripheral substitution on the morphology of the aggregates generated from these 1,2,4-triazoles is investigated by SEM imaging. The presence of paraffinic side chains results in long fibrillar supramolecular structures, but unsubstituted triazoles self-assemble into thinner ribbons and needle-like aggregates. The crystals obtained from methoxy-substituted triazoles have been utilised to elaborate a model that helps to justify aggregation of the investigated 1,2,4-triazoles, in which the operation of arrays of CH⋅⋅⋅π non-covalent interactions plays a significant role. The results presented herein demonstrate the ability of simple molecules to behave as multitasking scaffolds with different properties, depending on peripheral substitution. Thus, although 1,2,4-triazoles without long paraffinic side chains exhibit optical waveguiding behaviour, triazoles endowed with peripheral paraffinic side chains exhibit hexagonal columnar mesomorphism. [ABSTRACT FROM AUTHOR]

We have recently discovered significant amounts of zaccagnaite, a natural Zn-A1-CO3 hydrotalcite in the El Soplao cave (north Spain). The El Soplao zaccagnaite is speleothemic, i.e., formed in the cave, and therefore it represents a new cave mineral. The origin of E1 Soplao zaccagnaite is related to the diagenesis of Zn- and A1-rich ferromanganese speleo-stromatolites, where it occurs as a pore-filling cement that likely precipitated at low temperature (≤ ~ 11 °C). In some stromatolite layers, the abundance of zaccagnaite crystals is large enough to enable their physical separation. This has allowed us to obtain its X-ray powder-diffraction pattern, infrared spectrum, and differential thermal/thermogravimetric profiles. The cell parameters of the El Soplao zaccagnaite, refined from X-ray powder diffraction data are: a = 3.06616(1) and c = 22.6164(1) Å [α = β = 90°, γ = 120°; V = 184.139(1) ų; Z = 3], consistent with a new trigonal polytype of zaccagnaite: zaccagnaite-3R. Besides, the El Soplao zaccagnaite shows some features previously unknown in natural hydrotalcites, such as octahedral-like morphologies and fluorescence zoning. Electron microprobe analyses revealed that the El Soplao zaccagnaite-3R has an unusual chemistry for natural hydrotalcites, as it is significantly more rich in A1 (Zn2+/A13+ = 1.6) than the hexagonal (2H) polytype (Zn2+/A13+ = 2.0). The simplified chemical formula deduced from electron microprobe analysis is (Zn0.6A10.4)(OH)2(CO3)0.20.5H2O, where C and water were calculated by stoichiometry. The carbon content calculated by stoichiometry (2.2 wt%) is in good agreement with that measured with the electron microprobe on gold-coated samples (2.5 wt%). The presence of interlayer water and CO3 groups was confirmed by thermogravimetric analysis coupled to mass spectroscopy, and by the analysis of the infrared spectrum. [ABSTRACT FROM AUTHOR]

Abstract: In this paper we present the structural, magnetic and dielectric properties of ceramic nickel manganite NiMn2O4+δ produced by using nickel permanganate Ni(MnO4)2 xH2O as a precursor. We have characterized the NiMn2O4+δ stoichiometry using quantitative energy-dispersive analysis of X-rays and thermal gravimetry under reducing conditions. Increased oxygen and Mn4+ contents were detected. X-ray diffraction and Rietveld refinement of X-ray data were carried out. Temperature dependent magnetization measurements were performed and the ferri-magnetic transition was identified at ≈100K. The ferri-magnetic moment was found to be ≈1μ B and hysteretic magnetization vs applied field curves were obtained. Dielectric properties were measured using impedance spectroscopy. Two dielectric relaxation processes were detected, which were associated with grain boundary and bulk contributions. The Arrhenius plots of resistivity and the temperature dependent dielectric permittivity were obtained for the two relaxations by means of an equivalent circuit model based on a series of two parallel RC elements. [Copyright &y& Elsevier]

Ruddlesden-Popper oxides, (AO)(ABO 3 ) n , occupy a prominent place in the landscape of materials research because of their intriguing potential applications. Compositional modifications to the cation sublattices, A or B, have been explored in order to achieve enhanced functionalities. However, changes to the anionic sublattice have been much less explored. In this work, new oxygen-deficient manganese Ruddlesden-Popper-related phases, La 0.5 Ca 2.5 Mn 2 O 6.5 and La 0.5 Ca 2.5 Mn 2 O 6.25 , have been synthesized by controlled reduction of the fully oxidized n = 2 term La 0.5 Ca 2.5 Mn 2 O 7 . A complete structural and compositional characterization, by means of neutron diffraction, electron diffraction and atomically resolved scanning transmission electron microscopy and electron energy-loss spectroscopy techniques, allows the proposition of a topotactic reduction pathway through preferential oxygen removal in the [MnO 2 ] layers along [031] and [0{\bar 1}3] directions. The gradual decrease of the Mn oxidation state, accommodated by short-range ordering of anionic vacancies, reasonably explains the breaking of ferromagnetic interactions reinforcing the emergence of antiferromagnetic ones. Additional short-range order-disorder phenomena of La and Ca cations have been detected in the reduced La 0.5 Ca 2.5 Mn 2 O 7-δ , as previously reported in the parent compound.

The synthesis of a series of 4-aryl-3,5-bis(arylethynyl)aryl-4H-1,2,4-triazoles derivatives is reported and the influence exerted by peripheral substitution on the morphology of the aggregates generated from these 1,2,4-triazoles is investigated by SEM imaging. The presence of paraffinic side chains results in long fibrillar supramolecular structures, but unsubstituted triazoles self-assemble into thinner ribbons and needle-like aggregates. The crystals obtained from methoxy-substituted triazoles have been utilised to elaborate a model that helps to justify aggregation of the investigated 1,2,4-triazoles, in which the operation of arrays of C-H⋅⋅⋅π non-covalent interactions plays a significant role. The results presented herein demonstrate the ability of simple molecules to behave as multitasking scaffolds with different properties, depending on peripheral substitution. Thus, although 1,2,4-triazoles without long paraffinic side chains exhibit optical waveguiding behaviour, triazoles endowed with peripheral paraffinic side chains exhibit hexagonal columnar mesomorphism., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The twisting of supramolecular aggregates formed from simple linear bis(benzamides) has been investigated. The antiparallel arrangement of the amide functional groups controls the generation of twisted supramolecular structures. The results presented herein could contribute to elaborate predictive tools applicable in the generation of chiral supramolecular structures., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The self-assembly of triangular-shaped oligo(phenylene ethynylenes) (OPEs), peripherally decorated with chiral and linear paraffinic chains, is investigated in bulk, onto surfaces and in solution. Whilst the X-ray diffraction data for the chiral studied systems display a broad reflection centered at 2θ ∼20° (λ=Cu(Kα)), the higher crystallinity of OPE 3, endowed with three linear decyl chains, results in a diffractrogram with a number of well-resolved reflections that can be accurately indexed as a columnar packing arranged in 2D oblique cells. Compounds (S)-1 a and (R)-1 b-endowed with (S)- and (R)-3,7-dimethyloctyloxy chains-transfer their chirality to the supramolecular structures formed upon their self-assembly, and give rise to helical nanostructures of opposite handedness. A helicity switch is noticeable for the case of chiral (S)-2 decorated with (S)-2-methylnonyloxy chains which forms right-handed helices despite it possesses the same stereoconfiguration for their stereogenic carbons as (S)-1 a that self-assembles into left-handed helices. The stability and the mechanism of the supramolecular polymerization in solution have been investigated by UV/Vis experiments in methylcyclohexane. These studies demonstrate that the larger the distance between the stereogenic carbon and the aromatic framework is, the more stable the aggregate is. Additionally, the self-assembly mechanism is conditioned by the peripheral substituents: whereas compounds (S)-1 a and (R)-1 b self-assemble in a cooperative manner with a low degree of cooperativity, the aggregation of (S)-2 and 3 is well described by an isodesmic model. Therefore, the interaction between the chiral coil chains conditions the handedness of the helical pitch, the stability of the supramolecular structure and the supramolecular polymerization mechanism of the studied OPEs., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)