ABX-type hybrid organic-inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPhP)[Mn(dca)] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196-237 °C () and then vitrify upon cooling to room temperature, forming glasses.
View Article and Find Full Text PDFGe substitution into the recently discovered superionic conductor LiSiSI is demonstrated by synthesis of LiSiGeSI, where x≤1.2. The anion packing and tetrahedral silicon location of LiSiSI are retained upon substitution.
View Article and Find Full Text PDFExploration of compositional disorder using conventional diffraction-based techniques is challenging for systems containing isoelectronic ions possessing similar coherent neutron scattering lengths. Here, we show that a multinuclear solid-state Nuclear Magnetic Resonance (NMR) approach provides compelling insight into the Ga/Ge cation distribution and oxygen anion transport in a family of solid electrolytes with langasite structure and LaGaGeO composition. Ultrahigh field Ga Magic Angle Spinning (MAS) NMR experiments acquired at 35.
View Article and Find Full Text PDFFast cation transport in solids underpins energy storage. Materials design has focused on structures that can define transport pathways with minimal cation coordination change, restricting attention to a small part of chemical space. Motivated by the greater structural diversity of binary intermetallics than that of the metallic elements, we used two anions to build a pathway for three-dimensional superionic lithium ion conductivity that exploits multiple cation coordination environments.
View Article and Find Full Text PDFMultinuclear Nuclear Magnetic Resonance (NMR) spectroscopy of quadrupolar nuclei at ultrahigh magnetic field provides compelling insight into the short-range structure in a family of fast oxide ion electrolytes with LaSrGaO melilite structure. The striking resolution enhancement in the solid-state Ga NMR spectra measured with the world's unique series connected hybrid magnet operating at 35.2 T distinctly resolves Ga sites in four- and five-fold coordination environments.
View Article and Find Full Text PDFThe interface within a composite is critically important for the chemical and physical properties of these materials. However, experimental structural studies of the interfacial regions within metal-organic framework (MOF) composites are extremely challenging. Here, we provide the first example of a new MOF composite family, i.
View Article and Find Full Text PDFLayered tetrahedral network melilite is a promising structural family of fast ion conductors that exhibits the flexibility required to accommodate interstitial oxide anions, leading to excellent ionic transport properties at moderate temperatures. Here, we present a combined experimental and computational magic angle spinning (MAS) nuclear magnetic resonance (NMR) approach which aims at elucidating the local configurational disorder and oxide ion diffusion mechanism in a key member of this structural family possessing the LaSrGaO composition. O and Ga MAS NMR spectra display complex spectral line shapes that could be accurately predicted using a computational ensemble-based approach to model site disorder across multiple cationic and anionic sites, thereby enabling the assignment of bridging/nonbridging oxygens and the identification of distinct gallium coordination environments.
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