NdAgIn, orthorhombic, Imm2 (no. 44), a = 4.8608(4) & Aring;, b = 22.1322(6) & Aring;, c = 8.4137(8) & Aring;, V = 905.15(12) & Aring;3, Z = 12, Rgt (F) = 0.0449, wRref(F2) = 0.0544, T = 293 K.

BaSnO3 (BSO) and Cr-substituted BaSnO3 (1%, 3%, and 5%) perovskite samples were successfully synthesized by a chemical precipitation method. X-ray diffraction analysis confirmed the formation of a cubic perovskite structure in both unsubstituted and Cr-substituted BSO samples. The charge density distribution within the unit cell was visualized using the maximum entropy method (MEM), providing insight into the electronic structure and interatomic bonding. Urbach energy tails (BSOEU = 0.26 and BSOCr5EU = 0.68 eV) demonstrate the presence of structural disorder in the prepared perovskite samples. 119Sn M & ouml;ssbauer spectra underpin tetravalent tin in both samples. Density functional theory calculations show that unsubstituted BSO is a wide-bandgap, non-magnetic semiconductor, while Cr substitution introduces Cr-3d states that reduce the bandgap. The central substituted site is the most stable for Cr and shows strong spin polarization. However, this remains localized in the absence of defects. An oxygen vacancy near Cr significantly enhances and stabilizes this spin polarization, leading to more pronounced magnetic behavior. Together, our experimental results and DFT calculations show that Cr substitution effectively tunes the electronic structure, disorder, and magnetic behavior of BaSnO3, making it promising for optoelectronic applications.

This investigation focuses on the solid-state synthesis and a detailed structural and phase analytical investigation of the Co 𝑥 Ni 3−𝑥 Ga 4 series along a constant Ga compositional line within Co⎼Ni⎼Ga phase space. Combined analysis of single crystal X-ray diffraction and neutron powder diffraction of Co 𝑥 Ni 3−𝑥 Ga 4 , 𝑥 = 1.5 reveals a random distribution of Co and Ni over a single Wyckoff site, which contrasts with previous report suggesting atomic ordering. Phase analyses via X-ray powder diffraction indicates a vacancy order-disorder transition as the Co concentration increases beyond a critical limit. DFT calculation predicted a semi-metallic and nonmagnetic ground state, supported by the absence of magnetic peaks or intensity enhancement at 10 K neutron data compared to 300 K. Interestingly “Peierls-like” distortions are observed within the Ga substructure in the vacancy-ordered phase, whereas such distortions are absent in the vacancy-disordered phase. These distortions result in periodic charge localization and exhibit subtle alterations between room temperature and 180 K. Magnetic measurements further reveal cluster spin-glass behavior with a high coercivity. The non-trivial spin dynamics, coupled with large coercivity, makes this phase a compelling candidate for multifunctional applications.

The rare earth-rich intermetallic cadmium compounds RE 14 Ni 3 Cd 3 ( RE = Dy–Tm, Lu) were synthesized by induction melting of the elements in sealed tantalum ampoules, followed by annealing in sealed quartz tubes in muffle furnaces. The polycrystalline samples were characterized by powder X-ray diffraction, confirming isotypism with Gd 14 Co 3 In 2.7 , space group P 4 2 / nmc . The structures of the holmium and lutetium compound were refined from single-crystal X-ray diffractometer data: a = 945.03(3), c = 2,275.64(7) pm, w R 2 = 0.0316, 2800 F 2 values, 64 variables for Ho 14 Ni 3.70(1) Cd 2.27(1) and a = 929.79(3), c = 2,237.53(6) pm, w R 2 = 0.0537, 1315 F 2 values, 63 variables for Lu 14 Ni 3.69(3) Cd 2.31 . The striking structural feature of these cadmium phases is the formation of small defects on one 8 g nickel site and Cd/Ni mixing on the Wyckoff position 4 c . The complete RE 14 Ni 3 Cd 3 structures can be described by a condensation of tricapped trigonal prisms around the nickel and icosahedra around the cadmium atoms. Temperature dependent magnetic susceptibility studies have revealed Curie-Weiss paramagnetism for Ho 14 Ni 3 Cd 3 , Er 14 Ni 3 Cd 3 and Tm 14 Ni 3 Cd 3 with antiferromagnetic transitions in the low-temperature regime ( T N = 13.1(1), 8.6(1) and 3.6(1) K for RE = Ho, Er and Tm, respectively).

The rare earth-rich intermetallic cadmium compounds RE14Ni3Cd3 (RE = Dy-Tm, Lu) were synthesized by induction melting of the elements in sealed tantalum ampoules, followed by annealing in sealed quartz tubes in muffle furnaces. The polycrystalline samples were characterized by powder X-ray diffraction, confirming isotypism with Gd14Co3In2.7, space group P42/nmc. The structures of the holmium and lutetium compound were refined from single-crystal X-ray diffractometer data: a = 945.03(3), c = 2,275.64(7) pm, wR2 = 0.0316, 2800 F2 values, 64 variables for Ho14Ni3.70(1)Cd2.27(1) and a = 929.79(3), c = 2,237.53(6) pm, wR2 = 0.0537, 1315 F2 values, 63 variables for Lu14Ni3.69(3)Cd2.31. The striking structural feature of these cadmium phases is the formation of small defects on one 8g nickel site and Cd/Ni mixing on the Wyckoff position 4c. The complete RE14Ni3Cd3 structures can be described by a condensation of tricapped trigonal prisms around the nickel and icosahedra around the cadmium atoms. Temperature dependent magnetic susceptibility studies have revealed Curie-Weiss paramagnetism for Ho14Ni3Cd3, Er14Ni3Cd3 and Tm14Ni3Cd3 with antiferromagnetic transitions in the low-temperature regime (TN = 13.1(1), 8.6(1) and 3.6(1) K for RE = Ho, Er and Tm, respectively).

The platinides Nd5Sn9Pt7 and Gd5Sn9Pt7 were synthesized by arc-melting of the elements and subsequent annealing. Nd5Sn9Pt7 (a = 437.43(6) pm, b = 2872.2(4) pm, c = 727.8(1) pm) and Gd5Sn9Pt7 (a = 428.37(8) pm, b = 2869.7(5) pm, c = 720.4(1) pm) crystallize with the non-centrosymmetric Zr5Pd9P7-type structure, orthorhombic space group Amm2. The structure of the gadolinium compound was refined from single-crystal X-ray diffractometer data. Refinements of the occupancy parameters revealed the formation of tiny defects on four Wyckoff sites, leading to composition Gd4.95(1)Sn8.94(1)Pt6.89(2) for the studied crystal. The tin and platinum atoms build up a three-dimensional [Sn9Pt7]delta- polyanionic network with pronounced Sn-Pt bonding (264-289 pm). The Sn3 atoms show formation of a Sn3-Sn3 dumb-bell with a distance of 320 pm. The three crystallographically independent gadolinium atoms are located within distorted pentagonal prismatic channels. They are coordinated by the platinum and tin atoms: Gd1@Pt6Sn8, Gd2@Pt5Sn8 and Gd3@Pt5Sn8. Temperature-dependent magnetic susceptibility studies show Curie-Weiss paramagnetism for Gd5Sn9Pt7 and an experimental magnetic moment of 8.12(1) & micro;B per Gd atom, compatible with stable trivalent gadolinium. Gd5Sn9Pt7 is ordered antiferromagnetically below a N & eacute;el temperature of TN = 15.6(1) K.

Thus far, only a few sulfatomolybdates are known. Their anions feature mainly low dimensionalities. By choosing appropriate reaction conditions, new compounds, namely, β-K2[MoO2(SO4)2] and Na2[MoO2(SO4)2], are synthesised, which revealed layered structures for the first time for this class of materials. These compounds comprise sulfate tetrahedra and molybdate octahedra connected via common edges, forming a vierer ring between the building units. While the potassium cations are fully ordered in β-K2[MoO2(SO4)2], the sodium cations exhibit disorder in Na2[MoO2(SO4)2], which does not order at higher temperatures. Additionally, the compound crystallises in an incommensurate modulated structure at room temperature, which orders at higher temperatures. The titled compounds were characterised by single-crystal and powder XRD, MAPLE calculations, FT-IR spectroscopy, UV-vis spectroscopy, magnetic susceptibility analysis and thermogravimetric analysis (TGA). The latter reveals fairly high thermal stabilities for both compounds.

Reactions between carbon and lithium hydride in a mixed metal europium/lithium flux led to the synthesis of Eu2Li(C3)H. At room temperature, the compound crystallizes in the tetragonal space group P4/mbm (no. 127, Z = 2; Ca2Li(C3)H type) and undergoes a second-order structural phase transition below ∼250 K to an orthorhombic low-temperature modification (no. 55, Pbam; Z = 4), crystallizing in a new structure type. The phase transition was monitored by using single-crystal X-ray diffraction (SCXRD) and temperature-dependent high-resolution powder diffraction data. Infrared (IR) spectroscopy and gaschromatographic analysis (GC) of the hydrolysis products confirm the existence of a first europium compound with an allylenide anion (C34-). Magnetic susceptibility measurements and 151Eu Mössbauer spectroscopy reveal the presence of divalent europium, suggesting a charge-balanced carbide hydride (Eu2+)2(Li+)(C34-)(H-). A transition to a (soft) ferromagnetic ground state is observed below 42 K. In situ high-pressure, high-temperature (HPHT) investigations indicate a surprisingly high stability of Eu2Li(C3)H and yield a bulk modulus K0 = 65 GPa. Quantum chemical calculations (DFT + U) reveal a pseudogap at the Fermi level and allow the classification as a rare-earth metal Zintl phase exhibiting both ionic and covalent bonding contributions.

This study reports the synthesis of two rare-earth imidonitridophosphates and a series of 3d transition metal imidonitridophosphates (MIIIH3P6N12 with M = V, Cr, Eu, Lu, and MIIH4P6N12 with M = Mn, Fe, Co, Ni) by high-pressure metathesis. The crystal structures were elucidated by a combination of single-crystal and powder X-ray diffraction, elemental analysis, and vibrational spectroscopy. All compounds crystallize in the orthorhombic crystal system (transition metal imidonitridophosphates: Cmce, EuH3P6N12: Pna21, LuH3P6N12: Pbam) and feature a layered anionic network composed of vertex-sharing [PN4] tetrahedra. Magnetic measurements indicated that Mn, Fe, Co, and Ni are in the oxidation state + II, while V, Cr, Eu, and Lu are in the oxidation state + III. Furthermore, the measurements revealed paramagnetic behavior for all compounds except LuH3P6N12 and indications of antiferromagnetic ordering at low temperatures for NiH4P6N12 and CrH3P6N12. The oxidation states of Fe and Eu were further confirmed by Mössbauer spectroscopic measurements. As LuH3P6N12 does not exhibit paramagnetic behavior, additional NMR spectroscopic measurements were conducted. Furthermore, luminescence measurements provided information that supported the structural characterization and gave insights into the ligand field strength of the coordination sphere of the metal atoms in the considered imidonitridophosphates, indicating that the [PN4] units show weakened coordination behavior.

The series of platinum-rich rare earth intermetallics RE 6Pt13Zn4 (RE = Y, La-Nd, Sm, Gd-Ho) was synthesized by induction-melting of the elements in sealed niobium ampoules. X-ray powder data revealed isotypism with the sub-nitride Na16[Ba6N] according to Pt12Zn4[RE 6Pt] with platinum-zinc ordering on the two crystallographically independent sodium sites. The structure of Ho6Pt12.55(1)Zn4.45 was refined from single crystal X-ray diffractometer data: Im3 & strns;m, a = 941.36(2) pm, wR = 0.0312 for 172 F 2 values and 13 variables. Refinement of the occupancy parameters showed the formation of a small homogeneity range through Pt2/Zn mixing. The striking structural motif of the RE 6Pt13Zn4 series are Pt1 centered RE 6 octahedra in a bcc-type arrangement. These octahedra are surrounded by cages formed by the Pt2 and Zn atoms. Temperature dependent magnetic susceptibility measurements show stable trivalent rare earth ground states for all samples. Y6Pt13Zn4 and La6Pt13Zn4 show negative susceptibilities, i. e., the core diamagnetism overcompensates the Pauli contribution. Ferromagnetic ordering has been observed for RE = Ce (T C = 4.1(1) K), Pr (T C = 6.1(1) K), Nd (T C = 3.5(4) K), Sm (T C = 32.2(1) K), Gd (T C = 22.9(1) K) and Dy (T C = 5.7(1) K). Tb6Pt13Zn4 is the only antiferromagnet (T N = 8.7(1) K) and exhibits a metamagnetic transition at a critical field of 2.5(2) kOe. Ho6Pt13Zn4 shows no magnetic ordering down to 2 K.

Metalloid tin clusters represent an intriguing class of compounds that bridge molecular chemistry and the solid state, yet access to diverse examples remains limited. Herein, we present a mild, modular hydrostannolysis-type strategy that enables the synthesis of tin-based clusters stabilized by fairly small tert-butyl substituents, thereby overcoming the ligand-imposed structural limitations of established methodologies. The approach gave access to a series of clusters of different core sizes, including Sn11tBu12, featuring a [1.1.1]propellane-type backbone, as well as larger Sn15tBu14 and Sn16tBu16 derivatives adopting α-Sn-like core motifs with chair arrangement reminiscent of the diamond-type structure. Experimental characterization (X-ray crystallography and 119Sn Mössbauer spectroscopy) and computational analyses (NBO and QTAIM) corroborate near-zero charges at the apical tin centers; the frontier orbitals show pronounced multicenter character across the tin framework, and several deeper-lying orbitals exhibit "superatom"-like character. Additionally, this synthetic protocol also afforded a unique, heterobimetallic Sn/Pb spiro compound, revealing the compatibility of the method with multiple group 14 elements.

Mit M III M I [B(SO 4 ) 2 ] 4 (M III = Bi 3+ , Sb 3+ , Lu 3+ ; M I = H 3 O + , NO 2 + , Li + , Na + , K + , Rb + , Cs + ), das ein dreidimensionales Anion enthält, beschrieben wir kürzlich das erste Baukastensystem innerhalb der Chemie der Borosulfate. Hier beschreiben wir die entsprechende Reihe der Antimonverbindungen SbX[B(SO 4 ) 2 ] 4 (X = Li + , Na + , K + , Rb + , Cs + , Ag + , Tl + , NO + , NH 4 + ). Unter Beibehaltung derselben Anionentopologie kristallisieren die Verbindungen in den Raumgruppen I (Nr. 82), P (Nr. 81) und C 2 (Nr. 5), je nach Einfluss des freien Elektronenpaars des Antimons und der Größe der einwertigen Kationen. In dieser Arbeit wurden auch die Borosulfate SbX[B 4 O 2 (SO 4 ) 6 ] (X = Li + , Na + ) entdeckt. Diese weisen ein eindimensionales Anion auf, das B‐O‐B‐Brücken enthält, kristallisieren in Raumgruppe Pnma (Nr. 62) und bilden einen neuen Strukturtyp. 121 Sb‐Mößbauer‐Spektren zeigten für die Baukastenverbindungen zuvor noch nicht beobachtete negative Isomerieverschiebungen von nahezu ‐22 mm·s −1 , die eine sehr schwache Koordinationskraft des Borosulfatanions andeutet. Die Spektren wurden durch DFT‐Berechnungen bestätigt. In dieser Arbeit kamen zudem Einkristall‐Röntgendiffraktometrie, Infrarotspektroskopie, thermische Analyse und temperaturabhängige Röntgendiffraktometrie zum Einsatz.

The equiatomic plumbides SrPdPb and SrPtPb were synthesized by induction-melting of the elements in sealed tantalum ampoules followed by annealing in muffle furnaces. Both crystal structures were refined from single crystal X-ray diffractometer data: TiNiSi type, Pnma, a = 764.58(4), b = 478.23(7), c = 832.20(7) pm, wR2 = 0.0432, 643 F2 values, 20 variables for SrPdPb and a = 765.05(2), b = 476.31(3), c = 825.25(4), wR2 = 0.0691, 642 F2 values, 20 variables for SrPtPb. The palladium (platinum) and lead atoms built orthorhombically distorted and strongly puckered Pd3Pb3 (283-290 pm Pd-Pb) respectively Pt3Pb3 (281-291 pm Pt-Pb) hexagons that coordinate the strontium atoms.

Cadmium metal exhibits, in comparison with other metals, a low melting point of T = 594 K and exhibits a comparatively high vapor pressure. It therefore can be broadly used as a reactive flux medium for the growth of intermetallic phases. The results of phase-analytical investigations leading to new compounds, and of selected crystal growth experiments for direction dependent physical property studies are reviewed.

The group 14 tetrel elements C, Si, Ge, Sn and Pb need to accommodate four additional electrons to reach a full valence shell. However, despite fulfillment of the octet rule, tetra-anionic tetrels are highly reactive anions. The considerable 4- charge on single atoms dictates their chemistry, making such anions strongly reducing, Brønsted basic or nucleophilic. Magnesium salts of the tetra-anionic tetrels are generally known as Zintl phases which, under forced conditions, are only accessible for the heavier tetrels (Mg2E, E = Si-Pb). Here we report facile full reduction of Si, Ge, Sn or Pb precursors to tetra-anions using a molecular Mg0 complex at room temperature. The solubilized nature of the reducing agent allows for formation of hydrocarbon-soluble Zintl phases under mild conditions. Encapsulation of the tetrel tetra-anions in a metalla crown, a ring of metal cations, significantly contributes to their stabilization.

The cadmium-rich intermetallic cage compounds A Ir 2 Cd 20 ( A = Sr, La–Nd, Sm, Eu) were synthesized by induction-melting of the elements in sealed tantalum ampoules followed by annealing in muffle furnaces. The polycrystalline samples were characterized through their Guinier powder patterns. The structures of LaIr 2 Cd 20 and EuIr 2 Cd 20 were refined from single crystal X-ray diffractometer data: CeCr 2 Al 20 -type, Fd 3 ‾ $\overline{3}$ m , a = 1,566.26(4) pm, w R = 0.0438, 514 F 2 values, 17 variables for LaIr 2 Cd 20 and a = 1,567.58(3) pm, w R = 0.0645, 438 F 2 values, 17 variables for EuIr 2 Cd 20 . The structures derive from a MgCu 2 -type A Ir 2 substructure where the A atoms are surrounded by 16 Cd atoms in form of a Frank-Kasper polyhedron and the Ir atoms have 12 Cd neighbors in icosahedral coordination. Temperature dependent magnetic susceptibility studies show diamagnetism for SrIr 2 Cd 20 and LaIr 2 Cd 20 . CeIr 2 Cd 20 , PrIr 2 Cd 20 and NdIr 2 Cd 20 are Curie-Weiss paramagnets without any sign for magnetic ordering down to 2 K. EuIr 2 Cd 20 contains stable divalent europium (7.85(1) µ B Eu atom −1 ) and orders ferromagnetically at T C = 17.2(1) K. The stable divalent ground state is corroborated by 151 Eu Mössbauer spectroscopy with an isomer shift value of δ = −10.66(1) mm s −1 .

The MgCuAl2-type intermetallic phases CaPtIn2 and EuPtIn2 form a complete set of solid solutions Eu1-xCa x PtIn2 with a Vegard-type, almost linear decrease of the cell volume with increasing calcium content. The structure of Eu0.579(16)Ca0.421PtIn2 was refined from single-crystal X-ray diffractometer data: Amm2, a = 783.09(2), b = 442.91(6), c = 1,055.54(4) pm, wR = 0.0356, 1054 F2 values and 33 variables. This subgroup refinement yielded a europium accumulation on site 2a and a calcium accumulation on site 2b, pointing to an ordered arrangement. Temperature dependent magnetic susceptibility studies showed Curie-Weiss paramagnetism for all Eu1-xCa x PtIn2 samples. Ferromagnetic ordering is detected at low temperature with a decrease of the Curie temperature from 32.8(1) K for EuPtIn2 to 2.0(1) K for Eu0.1Ca0.9PtIn2. The decrease in TC proceeds in a sigmoidal manner with the inflection point close to the ordered composition Eu0.5Ca0.5PtIn2. The stable divalent europium ground states are corroborated by 151Eu M & ouml;ssbauer spectroscopy.

Lanthanides have seen rapid growth in the pharmaceutical and biomedical field, thus necessitating the development of hybrid metal–organic materials capable of exerting defined biological activities. Ternary hybrid lanthanide compounds were synthesized through reaction systems of Ln(III) (Ln = La, Nd, Eu) involving the antioxidant flavonoid chrysin (Chr) and 1,10-phenanhtroline (phen) under solvothermal conditions, thus leading to pure crystalline materials. The so-derived compounds were characterized physicochemically in the solid state through analytical (elemental analysis), spectroscopic (FT-IR, UV-visible, luminescence, ESI-MS, circular dichroism, 151Eu Mössbauer), magnetic susceptibility, and X-ray crystallographic techniques. The analytical and spectroscopic data corroborate the 3D structure of the mononuclear complex assemblies and are in line with theoretical calculations (Bond Valence Sum and Hirshfeld analysis), with their luminescence suggesting quenching on the flavonoid-phen electronic signature. Magnetic susceptibility data suggest potential correlations, which could be envisioned, supporting future functional sensors. At the biological level, the title compounds were investigated for their (a) ability to interact with bovine serum albumin and (b) antibacterial efficacy against Gram(−) (E. coli) and Gram(+) (S. aureus) bacteria, collectively revealing distinctly configured biological profiles and suggesting analogous applications in cellular (patho)physiologies.

The investigation focuses on Mn substitution in Co2Zn11, prepared by pursuing a solid-state sealed tube method under high vacuum. We report the crystal structure and magnetic properties of Co2Zn10.2Mn0.8 in detail. Co2Zn10.2Mn0.8 adopts the noncentrosymmetric space group I4̅3m (No. 217), and the distribution of Co, Mn, and Zn atoms is confirmed using X-ray and neutron powder diffraction (NPD) techniques. The magnetic studies reveal cluster glass (CG) formation below the spin-freezing temperature of 23.1 K in Co2Zn10.2Mn0.8, also indicated by the large value of the characteristic relaxation time (τ0) of ∼10-8 s. This large value of τ0 supports the formation of magnetic clusters. The magnetic moment primarily originates due to the spins of Mn atoms, which is realized from significant differences between majority- and minority-spin channels of Mn 3d states in the projected density of states curves.

We report on the synthesis an structural characterization of 16 new tetrelides RE -(Rh,Ir)-(Si,Ge), the phosphides Sm 4 Rh 13 P 9 , Sm 4 Ir 13 P 9 , Gd 4 Ir 13 P 9 and Yb 4 Ir 13 P 9 and the arsenide Eu 4 Ir 13 As 9 , which crystallize with the orthorhombic Ho 4 Ir 13 Ge 9 type. The structure of Gd 4 Ir 13 Ge 9 was refined from single-crystal X-ray diffractometer data: space group Pmmn , a = 397.76(2), b = 1,120.97(6), c = 1,935.52(10) pm, w R 2 = 0.0683, 2,537 F 2 values and 90 refined variables. The iridium and germanium atoms in Gd 4 Ir 13 Ge 9 build up a three-dimensional [Ir 13 Ge 9 ] polyanionic network which is stabilized by Ir–Ge (240–260 pm) and Ir–Ir (274–294 pm) bonding interactions. The three crystallographically independent gadolinium sites fill large channels within the [Ir 13 Ge 9 ] polyanionic network. They have hexagonal prismatic coordination with additional atoms capping the rectangular faces. The structural chemistry of the Ho 4 Ir 13 Ge 9 type is compared to the hexagonal phases RE 4 Co 13 (Si,P) 9 ( RE = Sm, Gd–Er), U 4 Fe 13 P 9 and the auride Sr 4 In 13 Au 9 . Magnetic susceptibility data of Tb 4 Ir 13 Ge 9 show Curie-Weiss behavior with an experimental magnetic moment of 10.4(1) µ B Tb atom −1 . Tb 4 Ir 13 Ge 9 is ordered antiferromagnetically at T N = 4.7(1) K and undergoes two successive metamagnetic steps.