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The cubic Laves-phase aluminides REAl2 with RE = Sc, Y, La, Yb and Lu were prepared from the elements by arc-melting or using refractory metal ampoules and induction heating. They all crystallize in the cubic crystal system with space group Fd[3 with combining macron]m and adopt the MgCu2 type structure. The title compounds were characterized by powder X-ray diffraction and spectroscopically investigated using Raman and 27Al and in the case of ScAl2 by 45Sc solid-state MAS NMR. In both, the Raman and NMR spectra, the aluminides exhibit only one signal due to the crystal structure. DFT calculations were used to calculate Bader charges illustrating the charge transfer in these compounds along with NMR parameters and densities of states. Finally, the bonding situation was assessed by means of ELF calculations rendering these compounds aluminides with positively charged REδ+ cations embedded in an [Al2]δ− polyanion.
Despite considerable interest in heteroatom-containing conjugated polymers, there are only few examples with heavier p-block elements in the conjugation path. The recently reported heavier acyclic diene metathesis (HADMET) allowed for the synthesis of a polymer containing Ge=Ge double bonds—albeit insoluble and with limited degree of polymerization. By incorporation of long alkyl chains, we now obtained soluble representatives, which exhibit degrees of polymerization near infinity according to diffusion-ordered NMR spectroscopy (DOSY) and dynamic light scattering (DLS). UV/Vis and NMR data confirm the presence of σ,π-conjugation across the silylene-phenylene linkers between the Ge=Ge double bonds. Favorable intermolecular dispersion interactions lead to ladder-like cylindrical assemblies as confirmed by X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and DLS. AFM and TEM images of deposited thin films reveal lamellar ordering of extended polymer bundles.
Block copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains.
The fabrication of nanocomposites containing magnetic nanoparticles is gaining interest as a model for application in small electronic devices. The self-assembly of block copolymers (BCPs) makes these materials ideal for use as a soft matrix to support the structural ordering of the nanoparticles. In this work, a high-molecular-weight polystyrene-b-poly(methyl methacrylate) block copolymer (PSb-PMMA) was synthesized through anionic polymerization. The influence of the addition of different ratios of PMMA-coated FePt nanoparticles (NPs) on the self-assembled morphology was investigated using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The selfassembly of the NPs inside the PMMA phase at low particle concentrations was analyzed statistically, and the negative effect of higher particle ratios on the lamellar BCP morphology became visible. The placement of the NPs inside the PMMA phase was also compared to theoretical descriptions. The magnetic addressability of the FePt nanoparticles inside the nanocomposite films was finally analyzed using bimodal magnetic force microscopy and proved the magnetic nature of the nanoparticles inside the microphase-separated BCP films.
Nominal CaAl2Pt2 and Ca2Al3Pt – two new Intermetallic Compounds in the Ternary System Ca−Al−Pt
(2024)
Single crystals of CaAl2Pt2, Ca2Al3Pt and Ca2AlPt2 were initially observed in an attempt to synthesize Ca3Al4Pt4. Their structures were determined using single-crystal X-ray diffraction experiments. While nominal CaAl2Pt2 (CaBe2Ge2 type, P4/nmm, a=426.79(2), c=988.79(6) pm, wR2=0.0679, 246 F2 values and 18 variables) and Ca2Al3Pt (Mg2Cu3Si type, P63/mmc, a=561.46(5), c=876.94(8) pm, wR2=0.0664, 214 F2 values and 13 variables) exhibit Al/Pt mixing, for Ca2AlPt2 (Ca2Ir2Si type, C2/c, a=981.03(2) b=573.74(1), c=772.95(2) pm, β=101.862(1)° wR2=0.0307, 2246 F2 values and 25 variables) no mixing was observed. Subsequently, the nominal compositions were targeted with synthetic attempts from the elements using arc-melting and annealing techniques. For CaAl2Pt2 and Ca2Al3Pt always multi-phase mixtures were observed while Ca2AlPt2 could be obtained as almost X-ray pure material. Quantum-chemical calculations were used to investigate the charge transfer in these compounds rendering them polar intermetallics with a designated [AlxPty]δ− polyanion and Caδ+ cations in the cavities of the polyanions.
Trotz erheblichen Interesses an heteroatomhaltigen konjugierten Polymeren sind Beispiele mit schwereren Elementen des p-Blocks im Konjugationspfad rar. Die kürzlich beschriebene Metathese schwererer acyclischer Diene (HADMET) ermöglichte die Synthese eines Ge=Ge-Doppelbindungen enthaltenden Polymers, wenn auch eines unlöslichen mit begrenztem Polymerisationsgrad. Durch Einführung langer Alkylketten erhielten wir nun lösliche Vertreter mit – nach diffusionsabhängiger NMR-Spektroskopie (DOSY) und dynamischer Lichtstreuung (DLS) – nahezu unendlichen Polymerisationsgraden. UV/Vis und NMR-Daten bestätigen das Vorliegen von σ,π-Konjugation entlang der Silylen-Phenylen-Verknüpfungen zwischen den Ge=Ge-Einheiten. Günstige intermolekulare Dispersionswechselwirkungen führen zu leiterartigen, zylindrischen Aggregaten, wie durch Röntgendiffraktometrie (XRD), Kleinwinkel-Röntgenstreuung (SAXS) und DLS bestätigt. AFM- und TEM-Bilder abgeschiedener dünner Schichten offenbaren eine lamellare Anordnung ausgedehnter Polymerbündel.
Inorganic-organic hybrid materials with redox-active components were prepared by an aqueous precipitation reaction of ammonium heptamolybdate (AHM) with para-phenylenediamine (PPD). A scalable and low-energy continuous wet chemical synthesis process, known as the microjet process, was used to prepare particles with large surface area in the submicrometer range with high purity and reproducibility on a large scale. Two different crystalline hybrid products were formed depending on the ratio of molybdate to organic ligand and pH. A ratio of para-phenylenediamine to ammonium heptamolybdate from 1 : 1 to 5 : 1 resulted in the compound [C6H10N2]2[Mo8O26] ⋅ 6 H2O, while higher PPD ratios from 9 : 1 to 30 : 1 yielded a composition of [C6H9N2]4[NH4]2[Mo7O24] ⋅ 3 H2O. The electrochemical behavior of the two products was tested in a battery cell environment. Only the second of the two hybrid materials showed an exceptionally high capacity of 1084 mAh g−1 at 100 mA g−1 after 150 cycles. The maximum capacity was reached after an induction phase, which can be explained by a combination of a conversion reaction with lithium to Li2MoO4 and an additional in situ polymerization of PPD. The final hybrid material is a promising material for lithium-ion battery (LIB) applications.
Molybdenum carbides, oxides, and mixed anionic carbide–nitride–oxides Mo(C,N,O)x are potential anode materials for lithium-ion batteries. Here we present the preparation of hybrid inorganic–organic precursors by a precipitation reaction of ammonium heptamolybdate ((NH4)6Mo7O24) with para-phenylenediamine in a continuous wet chemical process known as a microjet reactor. The mixing ratio of the two components has a crucial influence on the chemical composition of the obtained material. Pyrolysis of the precipitated precursor compounds preserved the size and morphology of the micro- to nanometer-sized starting materials. Changes in pyrolysis conditions such as temperature and time resulted in variations of the final compositions of the products, which consisted of mixtures of Mo(C,N,O)x, MoO2, Mo2C, Mo2N, and Mo. We optimized the reaction conditions to obtain carbide-rich phases. When evaluated as an anode material for application in lithium-ion battery half-cells, one of the optimized materials shows a remarkably high capacity of 933 mA h g−1 after 500 cycles. The maximum capacity is reached after an activation process caused by various conversion reactions with lithium.
