碱土金属铝酸盐系列长余辉磷光体的制备研究

研究了MAl2O4∶Eu2+(M=Ca,Sr,Ba)磷光体的制备过程,通过向磷光体中引入微量Dy3+,B3+等添加剂离子,得到了发绿色光的超长余辉磷光体,余辉发光初始亮度达4.8cd·m-2,激发停止50h后,其余辉发光仍清晰可见。制备出发紫色光、蓝色光及黄色光的碱土金属铝酸盐系列长余辉磷光体。分析了各磷光体发射光谱、激发光谱及余辉发光,讨论了磷光体的光谱移动以及Eu2+在碱土金属铝酸盐中的发光。     

Eu2+在碱土金属氟卤化物MFX(M=Ca、Sr或Ba,X=Cl、Br或I)中的发光

我们合成了六种Eu²⁺激活的碱土金属氟卤化物MFX:Eu²⁺(M=Ca、Sr或Ba;X=Cl、Br或I)。研究了它们的荧光发射光谱和激发光谱,讨论了Eu²⁺离子的跃迁发射随基质晶体组成和结构变化的规律。根据晶体场理论,按照C_4v点对称性,计算得到在MFCl:Eu²⁺(M=Ca、Sr或Ba)晶体中Eu²⁺离子的4?⁶5d¹激发态能级分裂的数值。     

New observations on the pressure dependence of luminescence from Eu2+-doped MF2 (M = Ca, Sr, Ba) fluorides

The luminescence from Eu(2+) ions in MF2 (M = Ca, Sr, Ba) fluorides has been investigated under the pressure range of 0-8 GPa. The emission band originating from the 4f(6)5d(1) --> 4f(7) transition of Eu(2+) ions in CaF2 and SrF2 shows the red-shift as increasing pressure with pressure coefficients of -17 meV/GPa for CaF2 and -18 meV/GPa for SrF2. At atmospheric pressure, the emission spectrum of BaF2:Eu(2+) comprises two peaks at 2.20 and 2.75 eV from the impurity trapped exciton (ITE) and the self-trapped exciton (STE), respectively. As the pressure is increased, both emission peaks shift to higher energies, and the shifting rate is slowed by the phase transition from the cubic to orthorhombic phase at 4 GPa. Due to the phase transition at 4-5 GPa pressure, the ITE emission disappears gradually, and the STE emission is gradually replaced by the 4f(6)5d(1) --> 4f(7) transition of Eu(2+). Above 5 GPa, the pressure behavior of the 4f(6)5d(1) --> 4f(7) transition of Eu(2+) in BaF2:Eu(2+) is the same as the normal emission of Eu(2+) in CaF2 and SrF2 phosphors.     

Extreme High-Voltage Electroconductivity of Molten KCl–MCl2 (M = Ca,Sr, Ba)

The electroconductivity of molten mixtures of calcium, strontium, and barium chlorides with potassium chloride (component concentrations 0, 25, 50, 75, 100 mol %) is studied as a function of the electric field strength. Isotherms of extreme high-voltage conductivities of the mixtures are an additive function of the composition, as opposed to isotherms of low-voltage conductivity, which exhibit considerable deviations and pass through minimums.     

The Periodate‐Based Double Perovskites M2NaIO6 (M = Ca,Sr, and Ba)

The crystal structures of the M₂NaIO₆ series (M = Ca, Sr, Ba), prepared at 650 °C by ceramic methods, were determined from conventional laboratory X‐ray powder diffraction data. Synthesis and crystal growth were made by oxidizing I^– with O₂^(air) to I⁷⁺ followed by crystal growth in the presence of NaF as mineralizator, or by the reaction of the alkali‐metal periodate with the alkaline‐earth metal hydroxide. All three compounds are insoluble and stable in water. The barium compound crystallizes in the cubic space group Fm3m (no. 225) with lattice parameters of a = 8.3384(1) Å, whereas the strontium and calcium compounds crystallize in the monoclinic space group P2₁/c (no. 14) with a = 5.7600(1) Å, b = 5.7759(1) Å, c = 9.9742(1) Å, β = 125.362(1)° and a = 5.5376(1) Å, b = 5.7911(1) Å, c = 9.6055(1) Å, β = 124.300(1)°, respectively. The crystal structure consists of either symmetric (for Ba) or distorted (for Sr and Ca) perovskite superstructures. Ba₂NaIO₆ contains the first perfectly octahedral [IO₆]^5– unit reported. The compounds of the ortho‐periodates are stable up to 800 °C. Spectroscopic measurements as well as DFT calculations show a reasonable agreement between calculated and observed IR‐ and Raman‐active vibrations.     

Kinetics of thermal decomposition of MCO3 to MO (M=Ca,Sr and Ba)

The kinetics of the thermal decompositions of CaCO₃, SrCO₃ and BaCO₃ into their oxides were studied by thermogravimetry at constant and linearly increasing temperatures. The kinetics of the isothermal decompositions of calcium and strontium carbonates were described by the lawR _n =1–(1–)^1/n , wheren=1.8 and 1.2, respectively. The kinetics of the non-isothermal decompositions of the two carbonates, analysed by the Ozawa and Coats-Redfern methods, were in keeping with the isothermal kinetics. True kinetic compensation laws were established for each decomposition of the two carbonates, including the data under both isothermal and non-isothermal conditions.As concerns the decompositions of BaCO₃, however, there was some difference between the kinetic features relating the isothermal and non-isothermal conditions. A true kinetic compensation law was not established in this case.

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Zusammenfassung Die Kinetik der thermischen Zersetzung von CaCO₃, SrCO₃ und BaCO₃ zu den Oxiden wurden durch Thermogravimetrie bei konstanter und linear ansteigender Temperatur untersucht. Die Kinetik der isothermen Zersetzung von Calcium- und Strontium-carbonat folgt dem GesetzR _n =1–(1 –)^1/n, won=1,8 bzw. 1,2. Die Kinetik der nichtisothermen nach den Methoden von Ozawa und Coats-Redfern analysierten Zersetzung der zwei Carbonate ist in Übereinstimmung mit der isothermen Zersetzung. Wahre kinetische Kompensationsgesetze wurden für die Zersetzung der beiden Carbonate erhalten, einschließlich der sich sowohl auf isotherme als auch auf nichtisotherme Bedingungen beziehenden Daten. Was die Zersetzung von Bariumcarbonat betrifft, so wurden einige Unterschiede im kinetischen Verhalten bei der Zersetzung unter isothermen und nichtisothermen Bedingungen festgestellt. Ein wahres kinetisches Kompensationsgesetz konnte in diesem Falle nicht ermittelt werden.

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, . R _n =1–(1–)^1/n , , , 1,8 1,2. , -, . « » , . , , . - «» .

     

MO-RE2O3-B2O3(M=Mg,Ca,Sr,Ba;RE=La,Eu,Gd)玻璃的发光性质

在空气中采用高温固相反应方法合成的17MO－（8-x-y)-75B2O3-xGd2O3(MLBEG,M-Mg,Ca,Sr,Ba)玻璃，在紫外光（λex=350nm)激发下发射蓝光和红光，在绿色光（λex=532nm)激发下发射红光，电子自旋共振谱研究表明玻璃体系中有Eu^2 离子存在，蓝色区的宽带发射是Eu^2 离子的5d-4f跃迁发射：红色区的窄带发射是Eu^3 离子的5Do-7FJ(J=1,2,3,4)跃迁发射，发现玻璃中的碱土金属离子对Eu^3 /Eu^2 离子的比例有很大影响，选择不同的碱土金属离子可以调节玻璃蓝色光和红色光的相对发射强度，MLBEG玻璃的发光性质可用于转换太阳能，增强植物的光合作用。     

掺杂铕和铽的卤硼酸盐荧光体的制备及光谱特征

采用高温固相法在空气中合成了一系列掺杂稀土离子的卤硼酸盐荧光体, 研究了其发光性质和基质组成对稀土离子共掺杂的荧光体发光性质的影响. 研究结果表明, 在Eu3+和Tb3+共掺杂的体系中存在电子转移, 因此出现了Eu3+, Eu2+和 Tb3+共存于同一基质共同发射的现象. Ce3+对Eu2+和Tb3+具有敏化作用, 可增强其发射强度. 基质的组成对稀土离子的发射峰位和发射强度有明显影响.     

Ce~（3＋）在钙钛矿型KMF_3（M＝Mg、Ca、Sr、Ba）基质中的发光特性

采用高温固相反应法，在Ａｒ气氛中合成了ＫＭＦ３（Ｍ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）基质化合物和掺杂Ｃｅ３＋的磷光体。经Ｘ射线衍射分析确定，ＫＭｇＦ３和ＫＣａＦ３属于立方晶系、钙钛矿型结构，ＫＳｒＦ３和ＫＢａＦ３具有类似的结构。测定了ＫＭＦ３∶Ｃｅ３＋的发光光谱，观察到与其结构对应的分为二种不同的光谱结构，讨论了Ｃｅ３＋的取代格位     

碱土金属钛酸盐-TiO2异质结型复合光催化活性研究

采用溶胶-凝胶法制备碱土金属钛酸盐MTiO3(M=Mg,Ca,Sr,Ba),并进一步与TiO2固相法复合制备MTiO3-TiO2异质结型复合光催化剂.以光催化降解亚甲基蓝(MB)为探针,评价了MTiO3和MTiO3-TiO2光催化剂的活性变化.结果表明,紫外光条件下碱土金属钛酸盐MTiO3的光催化活性顺序为:CaTiO3>BaTiO3>SrTiO3>MgTiO3,钙钛矿化合物的容忍因子、电负性以及催化剂的吸附性能都影响催化剂的降解效率.MTiO3与TiO2复合后形成的异质结复合光催化剂的催化活性得到显著的提高,催化剂浓度1.0g/L时,光催化反应1h后,MB(25mg/L)的降解率分别为82.6%,99.8%,93.7%,97.3%,异质结复合光催化剂活性顺序与MTiO3一致.光催化活性的提高与异质结界面形成电荷定向流动,促进光生电子、空穴的分离有关.     

EuAuGe Type Indides RAgIn (R = Ca,Sr, La,Eu)

The equiatomic intermetallic phases CaAgIn [a = 482.75(7), b = 750.0(1), c = 835.5(1) pm], SrAgIn [a = 495.86(5), b = 794.71(9), c = 851.89(9) pm], LaAgIn [a = 489.99(5), b = 767.93(9), c = 837.53(9) pm], and EuAgIn [a = 493.02(7), b = 781.6(1), c = 844.2(1) pm] were synthesized from the elements in sealed niobum containers. They crystallize with the EuAuGe type structure, space group Imm2. The four structures were refined from single‐crystal X‐ray data. The silver and indium atoms build up orthorhombically distorted, puckered Ag₃In₃ hexagons, which are stacked in AA′ sequence, leading to direct Ag–Ag and In–In interlayer bonding (e.g. 303 and 304 pm in CaAgIn). Temperature dependent magnetic susceptibility measurements show a magnetic moment of 7.40(1) μ_B per europium atom. EuAgIn orders antiferromagnetically at 5.7(5) K. The divalent nature of europium is also evident from ¹⁵¹Eu Mössbauer spectra: δ = –10.50(1) mm · s^–1 at 78 K.     

Contribution a l'etude des systemes Ca3(PO4)2-MSO4 (M=Sr,Ba)

In the systems Ca₃(PO₄)₂-MSO₄ (M = Sr, Ba), the series of single phase Ca_21?3xM_2xI(PO₄)_14?2x(SO₄)_2x with 0<x<0.15 forM=Sr and 0<x<0.1 forM = Ba have been prepared. These solid solutions, respectively strontium phosphosulfate and barium phosphosulfate, are isostructural with anhydrous tricalcium orthophosphate. They have been characterized by their infrared spectra and their crystallographic unit cell parameters.     

Nd0.67M0.33MnO3(M=Mg,Ca,Sr,Ba)的制备、结构与电性

本文通过共沉淀工艺合成了系列陶瓷化合物Nd_0.67M_0.33MnO₃(M=Mg,Ca,Sr,Ba)。与传统的陶瓷法相比，其成相温度降低了400℃。经X射线衍射分析表明，所得化合物为立方钙钛矿结构，各化合物的成相温度范围受碱土二价金属离子(M²⁺)的影响。样品的四极法电阻率测试结果表明：M²⁺的离子半径对样品的导电性起决定作用，并提出了反铁磁性(AF)与铁磁性(AF)等磁性结构假设，解释了该系列化合物的导电性。     

Bare and ligand protected planar hexacoordinate silicon in SiSb3M3+ (M = Ca,Sr, Ba) clusters

The occurrence of planar hexacoordination is very rare in main group elements. We report here a class of clusters containing a planar hexacoordinate silicon (phSi) atom with the formula SiSb₃M₃⁺ (M = Ca, Sr, Ba), which have D_3h (¹A₁′) symmetry in their global minimum structure. The unique ability of heavier alkaline-earth atoms to use their vacant d atomic orbitals in bonding effectively stabilizes the peripheral ring and is responsible for covalent interaction with the Si center. Although the interaction between Si and Sb is significantly stronger than the Si–M one, sizable stabilization energies (−27.4 to −35.4 kcal mol⁻¹) also originated from the combined electrostatic and covalent attraction between Si and M centers. The lighter homologues, SiE₃M₃⁺ (E = N, P, As; M = Ca, Sr, Ba) clusters, also possess similar D_3h symmetric structures as the global minima. However, the repulsive electrostatic interaction between Si and M dominates over covalent attraction making the Si–M contacts repulsive in nature. Most interestingly, the planarity of the phSi core and the attractive nature of all the six contacts of phSi are maintained in N-heterocyclic carbene (NHC) and benzene (Bz) bound SiSb₃M₃(NHC)₆⁺ and SiSb₃M₃(Bz)₆⁺ (M = Ca, Sr, Ba) complexes. Therefore, bare and ligand-protected SiSb₃M₃⁺ clusters are suitable candidates for gas-phase detection and large-scale synthesis, respectively.

The global minimum of SiSb₃M₃⁺ (M = Ca, Sr, Ba) is a D_3h symmetric structure containing an elusive planar hexacoordinate silicon (phSi) atom. Most importantly, the phSi core remains intact in ligand protected environment as well.

Exploring the bonding capacity of main-group elements (such as carbon or silicon) beyond the traditional tetrahedral concept has been a fascinating subject in chemistry for five decades. The 1970 pioneering work of Hoffmann and coworkers¹ initiated the field of planar tetracoordinate carbons (ptCs), or more generally, planar hypercoordinate carbons. The past 50 years have witnessed the design and characterization of an array of ptC and planar pentacoordinate carbon (ppC) species.^2–14 However, it turned out to be rather challenging to go beyond ptC and ppC systems. The celebrated CB₆²⁻ cluster and relevant species^15,16 were merely model systems because C avoids planar hypercoordination in such systems.^17,18 In 2012, the first genuine global minimum D_3h CO₃Li₃⁺ cluster was reported to have six interactions with carbon in planar form, although electrostatic repulsion between positively charged phC and Li centers and the absence of any significant orbital interaction between them make this hexacoordinate assignment questionable.¹⁹ It was only very recently that a series of planar hexacoordinate carbon (phC) species, CE₃M₃⁺ (E = S–Te; M = Li–Cs), were designed computationally by the groups of Tiznado and Merino (Fig. 1; left panel),²⁰ in which there exist pure electrostatic interactions between the negative C^δ− center and positive M^δ+ ligands. These phC clusters were achieved following the so-called “proper polarization of ligand” strategy.Open in a separate windowFig. 1The pictorial depiction of previously reported phC CE₃M₃⁺ (E = S–Te; M = Li–Cs) clusters and the present SiE₃M₃⁺ (E = S–Te and N–Sb; M = Li–Cs and Ca–Ba) clusters. Herein the solid and dashed lines represent covalent and ionic bonding, respectively. The opposite double arrows illustrate electrostatic repulsion.The concept of planar hypercoordinate carbons has been naturally extended to their next heavier congener, silicon-based systems. Although the steric repulsion between ligands decreases due to the larger size, the strength of π- and σ-bonding between the central atom and peripheral ligands dramatically decreases, which is crucial for stability. Planar tetracoordinate silicon (ptSi) was first experimentally observed in a pentaatomic C_2v SiAl₄⁻ cluster by Wang and coworkers in 2000.²¹ Very recently, this topic got a huge boost by the room-temperature, large-scale syntheses of complexes containing a ptSi unit.²² A recent computational study also predicted the global minimum of SiMg₄Y⁻ (Y = In, Tl) and SiMg₃In₂ to have unprecendented planar pentacoordinate Si (ppSi) units.²³ Planar hexacoordinate Si (phSi) systems seem to be even more difficult to stabilize. Previously, a C_2v symmetric Cu₆H₆Si cluster was predicted as the true minimum,²⁴ albeit its potential energy surface was not fully explored. A kinetically viable phSi SiAl₃Mg₃H₂⁺ cluster cation was also predicted.²⁵ However, these phSi systems^24,25 are only local minima and not likely to be observed experimentally. In 2018, the group of Chen identified the Ca₄Si₂²⁻ building block containing a ppSi center and constructed an infinite CaSi monolayer, which is essentially a two-dimensional lattice of the Ca₄Si₂ motif.²⁶ Thus, it is still an open question to achieve a phSi atom to date.Herein we have tried to find the correct combination towards a phSi system as the most stable isomer. Gratifyingly, we found a series of clusters, SiE₃M₃⁺ (E = N, P, As, Sb; M = Ca, Sr, Ba), having planar D_3h symmetry with Si at the center of the six membered ring, as true global minimum forms. Si–E bonds are very strong in all the clusters, and alkaline-earth metals interact with the Si center by employing their d orbitals. However, electrostatic repulsion originated from the positively charged Si and M centers for E = N, P, and As dominates over attractive covalent interaction, making individual Si–M contacts repulsive in nature. This makes the assignment of SiE₃M₃⁺ (E = N, P, As; M = Ca, Sr, Ba) as genuine phSi somewhat skeptical. SiSb₃M₃⁺ (M = Ca, Sr, Ba) clusters are the sole candidates which possess genuine phSi centers as both electrostatic and covalent interactions in Si–M bonds are attractive. The d orbitals of M ligands play a crucial role in stabilizing the ligand framework and forming covalent bonds with phSi. Such planar hypercoordinate atoms are, in general, susceptible to external perturbations. However, the present title clusters maintain the planarity and the attractive nature of the bonds even after multiple ligand binding at M centers in SiSb₃M₃(NHC)₆⁺ and SiSb₃M₃(Bz)₆⁺. This would open the door for large-scale synthesis of phSi as well.Two major computational efforts were made before reaching our title phSi clusters. The first one is to examine SiE₃M₃⁺ (E = S–Po; M = Li–Cs) clusters, which adopt D_3h or C_3v structures as true minima (see Table S1 in ESI^†), being isoelectronic to the previous phC CE₃M₃⁺ (E = S–Po; M = Li–Cs) clusters. In the SiE₃M₃⁺ (E = S–Po; M = Li–Cs) clusters, the Si center always carries a positive charge ranging from 0.01 to +1.03|e|, in contrast to the corresponding phC species (see Fig. 1). Thus, electrostatic interactions between the Si^δ+ and M^δ+ centers would be repulsive (Fig. 1). Given that the possibility of covalent interaction with an alkali metal is minimal, it would be a matter of debate whether they could be called true coordination. A second effort is to tune the electronegativity difference between Si and M centers so that the covalent contribution in Si–M bonding becomes substantial. Along this line, we consider the combinations of SiE₃M₃⁺ (E = N, P, As, Sb; M = Be, Mg, Ca, Sr, Ba). The results in Fig. S1^† show that for E = Be and Mg, the phSi geometry has a large out-of-plane imaginary frequency mode, which indicates a size mismatch between the Si center and peripheral E₃M₃ (E = N–Bi; M = Be, Mg) ring. On the other hand, the use of larger M = Ca, Sr, Ba atoms effectively expands the size of the cavity and eventually leads to perfect planar geometry with Si atoms at the center as minima. In the case of SiBi₃M₃⁺, the planar isomer possesses a small imaginary frequency for M = Ca. Although planar SiBi₃Sr₃⁺ and SiBi₃Ba₃⁺ are true minima, they are 2.2 and 2.5 kcal mol⁻¹ higher in energy than the lowest energy isomer, respectively (Fig. S2^†). Fig. 2 displays some selected low-lying isomers of SiE₃M₃⁺ (E = N, P, As, Sb; M = Ca, Sr, Ba) clusters (see Fig. S3–S6^† for additional isomers). The global minimum structure is a D_3h symmetric phSi with an ¹A₁′ electronic state for all the twelve cases. The second lowest energy isomer, a ppSi, is located more than 49 kcal mol⁻¹ above phSi for E = N. This relative energy between the most stable and nearest energy isomer gradually decreases upon moving from N to Sb. In the case of SiSb₃M₃⁺ clusters, the second-lowest energy isomer is 4.6–6.1 kcal mol⁻¹ higher in energy than phSi. The nearest triplet state isomer is very high in energy (by 36–53 kcal mol⁻¹, Fig. S3–S6^†) with respect to the global minimum.Open in a separate windowFig. 2The structures of low-lying isomers of SiE₃M₃⁺ (E = N, P, As, Sb; M = Ca, Sr, Ba) clusters. Relative energies (in kcal mol⁻¹) are shown at the single-point CCSD(T)/def2-TZVP//PBE0/def2-TZVP level, followed by a zero-energy correction at PBE0. The values from left to right refer to Ca, Sr, and Ba in sequence. The group symmetries and electronic states are also given.Born–Oppenheimer molecular dynamics (BOMD) simulations at room temperature (298 K), taking SiE₃Ca₃⁺ clusters as case studies, were also performed. The results are displayed in Fig. S7.^† All trajectories show no isomerization or other structural alterations during the simulation time, as indicated by the small root mean square deviation (RMSD) values. The BOMD data suggest that the global minimum also has reasonable kinetic stability against isomerization and decomposition.The bond distances, natural atomic charges, and bond indices for SiE₃Ca₃⁺ clusters are given in † for M = Sr, Ba). The Si–E bond distances are shorter than the typical Si–E single bond distance computed using the self-consistent covalent radii proposed by Pyykkö.²⁷ In contrast, the Si–M bond distance is almost equal to the single bond distance. This gives the first hint of the presence of covalent bonding therein. However, the Wiberg bond indices (WBIs) for the Si–M links are surprisingly low (0.02–0.04). We then checked the Mayer bond order (MBO), which can be seen as a generalization of WBIs and is more acceptable since the approach of WBI calculations assumes orthonormal conditions of basis functions while the MBO considers an overlap matrix. The MBO values for the Si–M links are now sizable (0.13–0.18). These values are reasonable considering the large difference in electronegativity between Si and M, and, therefore, only a very polar bond is expected between them. In fact, the calculations of WBIs after orthogonalization of basis functions by the Löwdin method gives significantly large bond orders (0.48–0.55), which is known to overestimate the bond orders somewhat. The above results indicate that the presence of covalent bonding cannot be ruled out only by looking at WBI values.Bond distances (r, in Å), different bond orders (WBIs) {MBOs} [WBI in orthogonalized basis], and natural atomic charges (q, in |e|) of SiE₃Ca₃⁺ (E = N, P, As, Sb) clusters at the PBE0/def2-TZVP level

MZrO3（M=Ba,Sr,Ca）水热合成中结构与反应活性的关系

ＭＺｒＯ_３（Ｍ＝Ｂａ，Ｓｒ，Ｃａ）水热合成中结构与反应活性的关系郑文君，庞文琴（吉林大学化学系，长春，１３００２３）关键词水热合成，ＭＺｒＯ_３（Ｍ＝Ｂａ，Ｓｒ，Ｃａ），结构，反应活性钙钛矿型复合氧化物ＭＺｒＯ３（Ｍ＝Ｂａ，Ｓｒ，Ｃａ）是重要的功能陶...     

Structure Prediction of Binary Pernitride MN2 Compounds (M=Ca,Sr, Ba,La, and Ti)

Metal‐pernitride compounds belong to a class of chemical systems in which both the complex ions and the non‐bonding electrons may play roles in the formation of their modified crystalline structures. To investigate this issue, the energy landscapes of pernitrides of metals with different maximum valence (M=Ca, Sr, Ba, La, and Ti) were globally explored on the ab initio level at standard and high pressures, thereby yielding possible (meta)stable modifications in these systems together with information on how the landscape changed as function of the valence of the metal cation. For all of the systems in which no compounds had been synthesized so far, we predicted the existence of kinetically stable modifications that should, in principle, be experimentally accessible. In particular, TiN₂ should crystallize in a new structure type, TiN₂‐I.     

Magnetic Investigations and 151Eu Mössbauer Spectroscopy of MYbSi4N7 with M = Sr,Ba, Eu

The isotypic nitridosilicates MYb[Si₄N₇] (M = Sr, Ba, Eu) were obtained by the reaction of the respective metals with Si(NH)₂ in a radiofrequency furnace below 1600 °C. On the basis of powder diffraction data of MYb[Si₄N₇] Rietveld refinements of the lattice constants were performed; these confirmed the previously published single‐crystal data. The compounds contain a condensed network of corner‐sharing [N(SiN₃)₄] units. The central nitrogen thus exhibits ammonium character. Magnetic susceptibility measurements of MYb[Si₄N₇] (M = Sr, Ba, Eu) show paramagnetic behavior with experimental magnetic moments of 3.03(2), (Sr), 2.73(2) (Ba), and 9.17(2) (Eu) μ_B per formula unit. In EuYbSi₄N₇ the europium and ytterbium atoms are in stable divalent and trivalent states, respectively. According to the non‐magnetic character of the alkaline earth cations, ytterbium has to be in an intermediate valence state Yb^III‐x in the strontium and barium compound. Consequently, either a partial exchange N^3—/O^2— resulting in compositions MYb^III‐x[Si₄N_7—xO_x] or an introduction of anion defects according to MYb^III‐x[Si₄N_7—x/3□_x/3] has to be assumed. The phase width 0 ≤ x ≤ 0.4 was estimated according to the magnetic measurements. ¹⁵¹Eu Mössbauer spectra of EuYb[Si₄N₇] at 78 K show a single signal at an isomer shift of δ = —12.83(3) mm s^—1 subject to quadrupole splitting of ΔE_Q = 5.7(8) mm s^—1, compatible with purely divalent europium.     

Valence compounds versus metals. Synthesis, characterization, and electronic structures of cubic Ae(4)Pn(3) phases in the systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

The isostructural compounds Sr(4)Bi(3), Ba(4)Bi(3), and Ba(4)As( approximately )(2.60) were prepared by direct reactions of the corresponding elements and their structures determined from single-crystal X-ray diffraction data as anti-Th(3)P(4) type in the cubic space group I43d, Z = 4 (a = 10.101(1) A, 10.550(1) A, 9.973 (1) A, respectively). The two bismuth compounds are stoichiometric, and the arsenide refines as Ba(4)As(2.60(2)). Only unrelated phases are obtained for all binary combinations among the title components for either Ca or Sb. The magnetic susceptibility and resistivities of Ba(4)Bi(3) and Eu(4)Bi(3) show that they are good metallic conductors ( approximately 40 microomega.cm at 298 K), whereas Ba(4)As(2.60) exhibits rho(150) > 1000 microomega.cm. The electronic structures of Sr(4)Bi(3), Ba(4)Bi(3), and Ba(4)As(3) were calculated by TB-LMTO-ASA methods. Mixing of cation d states into somewhat disperse valence p bands on Bi results in empty bands at E(F) and metallic behavior, whereas the narrower valence band in the electron-deficient Ba(4)As(3) leads to vacancies in about 11% of the anion sites and a valence compound.