The high pressure properties of the novel tetrel-free clathrate, Ba₈Cu13.1Zn3.3P29.6, were investigated using synchrotron powder X-ray diffraction. The pressure was applied using a diamond anvil cell. No structural transitions or decomposition were detected in the studied pressure range of 0.1-7 GPa. The calculated bulk modulus for Ba₈Cu13.1Zn3.3P29.6 using a third-order Birch-Murnaghan equation of state is 65(6) GPa at 300 K. This bulk modulus is comparable to the bulk moduli of Ge- and Sn-based clathrates, like A₈Ga16Ge30 (A = Sr, Ba) and Sn19.3Cu4.7P22I₈, but lower than those for the transition metal-containing silicon-based clathrates, Ba₈TxSi46-x, T = Ni, Cu; 3 ≤ x ≤ 5.

The title compound, [Co(II)(C2H8N2)3]Cl2, was obtained unexpectedly as the product of an attempted solvothermal synthesis of cobalt selenide from the elements in the presence of NH4Cl in ethyl-enedi-amine solvent. The three chelate rings of the distorted octa-hedral [Co(C2H8N2)3](2+) complex cation adopt twisted conformations about their C-C bonds. The spread of cis-N-Co-N bond angles [80.17 (6)-98.10 (6)°] in the title compound is considerably greater than the equivalent data for [Co(III)(C2H8N2)3]Cl3 [Takamizawa et al. (2008 ▶). Angew. Chem. Int. Ed. 47, 1689-1692]. In the crystal, the components are linked by numerous N-H⋯Cl hydrogen bonds, generating a three-dimensional network in which the cationic complexes are stacked in columns along [010] and separated by columns of chloride anions.

The first arsenic-based clathrate exhibiting superstructural ordering due to optimization of Au-As, As-As, and Ba-Au bonding is reported. Ba₈Au₁₆As₃₀ crystallizes in a unique P2₁/c monoclinic clathrate structure. The synthesis, crystal and electronic structure, and transport properties are discussed.

A new type-I clathrate, Ba₈Cu₁₄Ge₆P₂₆, was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba₈Cu₁₄Ge₆P₂₆ crystallizes in the cubic space group Pm3n (no. 223). Ba₈Cu₁₄Ge₆P₂₆ is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba₈Cu₁₄Ge₆P₂₆ were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba₈Cu₁₄Ge₆P₂₆ is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m^-1 K^-1 at 812 K. The thermoelectric figure of merit, ZT, for a slice of the Bridgman-grown crystal of Ba₈Cu₁₄Ge₆P₂₆ approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm^-1 K^-2. The thermoelectric efficiency of Ba₈Cu₁₄Ge₆P₂₆ is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700-850 K temperature region, including all tetrel-free clathrates. Ba₈Cu₁₄Ge₆P₂₆ expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba₈Cu₁₄Ge₆P₂₆ a strong candidate as a novel and efficient thermoelectric material.

The synthesis, structural characterization, and optical properties of the binary Zintl phases of α-EuP₃, β-EuP₃, EuP₂, and α-K₄P₆ are reported in this study. These crystal structures demonstrate the versatility of P fragments with dimensionality varying from 0D (P₆ rings in α-K₄P₆) to 1D chains (EuP₂) to 2D layers (both EuP₃). EuP₂ is isostructural to previously reported SrP₂ and BaP₂ compounds. The thermal stabilities of the EuP₂ and both EuP₃ phases were determined using differential scanning calorimetry (DSC), with melting temperatures of 1086 K for the diphosphide and 1143 K for the triphosphides. Diffuse reflectance spectroscopy indicated that EuP₂ is an indirect semiconductor with a direct bandgap of 1.12(5) eV and a smaller indirect one, less than 1 eV. Both EuP₃ compounds had bandgaps smaller than 1 eV.

A novel mixed-valent hybrid chiral and polar compound, Fe₇As₃Se₁₂(en)₆(H₂O), has been synthesized by a single-step solvothermal method. The crystal structure consists of 1D [Fe₅Se₉] chains connected via [As₃Se₂]-Se pentagonal linkers and charge-balancing interstitial [Fe(en)₃]²⁺ complexes (en = ethylenediamine). Neutron powder diffraction verified that interstitial water molecules participate in the crystal packing. Magnetic polarizability of the produced compound was confirmed by X-ray magnetic circular dichroism (XMCD) spectroscopy. X-ray absorption spectroscopy (XAS) and ⁵⁷Fe Mössbauer spectroscopy showed the presence of mixed-valent Fe²⁺/Fe³⁺ in the Fe-Se chains. Magnetic susceptibility measurements reveal strong antiferromagnetic nearest neighbor interactions within the chains with no apparent magnetic ordering down to 2 K. Hidden short-range magnetic ordering below 70 K was found by ⁵⁷Fe Mössbauer spectroscopy, showing that a fraction of the Fe³⁺/Fe²⁺ in the chains are magnetically ordered. Nevertheless, complete magnetic ordering is not achieved even at 6 K. Analysis of XAS spectra demonstrates that the fraction of Fe³⁺ in the chain increases with decreasing temperature. Computational analysis points out several competing ferrimagnetic ordered models within a single chain. This competition, together with variation in the Fe oxidation state and additional weak intrachain interactions, is hypothesized to prevent long-range magnetic ordering.

To investigate magnetostructural relationships in colloidal magnetite (Fe₃O₄) nanoparticles (NPs) at high temperature (300-900 K), we measured the temperature dependence of magnetization (M) of oleate-capped magnetite NPs ca. 20 nm in size. Magnetometry revealed an unusual irreversible high-temperature dependence of M for these NPs, with dip and loop features observed during heating-cooling cycles. Detailed characterizations of as-synthesized and annealed Fe₃O₄ NPs as well as reference ligand-free Fe₃O₄ NPs indicate that both types of features in M(T) are related to thermal decomposition of the capping ligands. The ligand decomposition upon the initial heating induces a reduction of Fe³⁺ to Fe²⁺ and the associated dip in M, leading to more structurally and compositionally uniform magnetite NPs. Having lost the protective ligands, the NPs continually sinter during subsequent heating cycles, resulting in divergent M curves featuring loops. The increase in M with sintering proceeds not only through elimination of a magnetically dead layer on the particle surface, as a result of a decrease in specific surface area with increasing size, but also through an uncommonly invoked effect resulting from a significant change in Fe³⁺/Fe²⁺ ratio with heat treatment. The interpretation of irreversible features in M(T) indicates that reversible M(T) behavior, conversely, can be expected only for ligand-free, structurally and compositionally uniform magnetite NPs, suggesting a general applicability of high-temperature M(T) measurements as an analytical method for probing the structure and composition of magnetic nanomaterials.

Ambient energy harvesting has great potential to contribute to sustainable development and address growing environmental challenges. Converting waste energy from energy-intensive processes and systems (e.g. combustion engines and furnaces) is crucial to reducing their environmental impact and achieving net-zero emissions. Compact energy harvesters will also be key to powering the exponentially growing smart devices ecosystem that is part of the Internet of Things, thus enabling futuristic applications that can improve our quality of life (e.g. smart homes, smart cities, smart manufacturing, and smart healthcare). To achieve these goals, innovative materials are needed to efficiently convert ambient energy into electricity through various physical mechanisms, such as the photovoltaic effect, thermoelectricity, piezoelectricity, triboelectricity, and radiofrequency wireless power transfer. By bringing together the perspectives of experts in various types of energy harvesting materials, this Roadmap provides extensive insights into recent advances and present challenges in the field. Additionally, the Roadmap analyses the key performance metrics of these technologies in relation to their ultimate energy conversion limits. Building on these insights, the Roadmap outlines promising directions for future research to fully harness the potential of energy harvesting materials for green energy anytime, anywhere.