ALa9(SiO4)6O2.5(A=Ca，Sr，Ba)的合成及其电性能

利用溶胶-凝胶法在850 ℃合成了硅酸盐氧基磷灰石ALa₉(SiO₄)₆O_2.5(A=Ca、Sr和Ba),经XRD表征所得产品为磷灰石相。以电化学阻抗谱研究了ALa₉(SiO₄)₆O_2.5的导电性能,发现A的原子半径越大,体系的电导率越高,活化能却减小。在700 ℃时BaLa₉(SiO₄)     

Phase formation in Li2MoO4-Rb2MoO4-MMoO4 (M = Ca, Sr, Ba, Pb) systems and the crystal structure of α-Rb2Pb(MoO4)2

A subsolidus triangulation of Li₂MoO₄-Rb₂MoO₄-MMoO₄ (M = Ca, Sr, Pb, Ba) systems is performed. The RbLiMoO₄-Rb₂M(MoO₄)₂ (M = Pb, Ba) joins, where 11 mol.% long Rb₂M(MoO₄)₂-based solid solutions are found, are studied in most detail. Ternary molybdates do not form in the systems, which is confirmed by spontaneous flux crystallization. The α-Rb₂Pb(MoO₄)₂ crystals are obtained and their crystal structure is solved (a = 20.9724(15) ?, b = 12.1261(8) ?, c = 16.1171(10) ?, β = 115.728(13)°, C2/m space group, R = 0.0695, Z = 16), which is a monoclinic superstructure of the palmierite type and has the largest cell volume and the most complex structure among lead-containing palmierites. One of the MoO₆ tetrahedra is orientationally disordered over two sites; lead atoms are shifted from the centers of their coordination polyhedra to one of their faces and have cn = 6–8; for rubidium cations cn = 10–12.     

M5(PO4)3F (M=Ca, Sr, Ba)中Sm3+的电荷迁移态及Sm3+和Eu3+的电荷迁移能量关系

采用高温固相反应合成了M_5-2xSm_xNa_x(PO₄)₃F(M=Ca,Sr,Ba)荧光体,研究了其在真空紫外-可见光范围的发光特性。发现在Ca₅(PO₄)₃F中Sm³⁺的电荷迁移带约在191 nm,在Sr₅(PO₄)₃F中约在199 nm,而在Ba₅(PO₄)₃F中约在204 nm,随着被取代碱土离子半径的增大电荷迁移能量逐渐减小。比较了M₅(PO₄)₃F (M=Ca,Sr,Ba)中Sm³⁺和Eu³⁺电荷迁移能量的关系。     

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。     

Electroconductivity of Solid Solutions Cs3–2x M x PO4 (M = Ba, Sr, Ca, Mg)

Solid solutions Cs_{3 – 2x} M _x PO₄ (M = Ba, Sr, Ca, Mg) are synthesized and their thermal behavior and electroconductivity are examined. Adding elements of Subgroup IIA of the periodic table into cesium orthophosphate shifts the phase transition, which occurs in pure Cs₃PO₄ at 450–620°, towards lower temperatures and raises the cesium cation conductivity at low temperatures. The electroconductivity of a high-temperature modification of Cs₃PO₄ is weakly dependent on the presence and concentration of such additives, which points to structural disordering of the cesium sublattice.     

(Ca,Me)La4Si3O13:Eu3+(Me=Sr,Ba)荧光粉的结构和发光特性

采用高温固相法制备了(Ca,Me)La4Si3O13∶Eu3+(Me=Sr,Ba)系列红色荧光体,考察了Eu3+掺杂浓度和Sr2+,Ba2+置换对荧光体结构和发光特性的影响。Eu3+最佳掺杂浓度为nEu3+∶nLa3+=1∶7,5D0-7F2与5D0-7F1跃迁发射强度比为2.55。Eu3+掺杂使晶胞参数a和c呈线性变小,对c的影响大于a,使a/c比增大。Sr2+和Ba2+分别置换基质中的Ca2+可以形成完全固溶体,晶胞参数随Sr2+或Ba2+的置换量增加呈线性增大,使a/c比减小。各发射峰强度在Sr2+置换量为0.4 mol时出现极大值,但随Ba2+置换量的增加而不断增强,全置换后荧光强度最大。荧光体的色坐标为(0.638 5,0.353 0)。     

Tb3+在MO(M=Ca,Sr)中的长余辉发光

长余辉发光材料的研究与应用，已有近100年的历史，目前仍在许多领域中有着重要应用。此类材料与其他光致发光材料具有相同的发光性能．只是更注重其发光的衰减过程和热释光性能。如．ZnS：Cu作为黄绿色的长余辉发光材料，在1992年以前是余辉性能最好的长余辉发光材料，一直处于发光研究工作的中心。     

MMgF4(M=Ca,Sr, Ba)体系中Eu和Tb的电荷迁移

于不同气流中, 合成了MMgF4:xEu,yTb复合氟化物磷光体。该体系中Eu^3^+和Eu^2^+共存。Tb的存在影响Eu的价态存在形式。ESR测试表明, 随Tb的掺入浓度增加, Eu^2^+的浓度呈规律性变化。随Eu的掺入, 样品的XPS谱中出现了四价铽的Tb3d5/2特征伴峰。认为Eu^3^+和Tb^3^+之间存在电荷迁移平衡。即Eu^3^++Tb^3^+=Eu^2^++Tb^4^+。通过半定量手段研究了SrMgF4中这一衡的平衡常数。     

X-ray study of M(Aet)2·8H2O (M = Sr, Ba) and the crystal structure of [Sr(Aet)(OH2)5](Aet)·3H2O

An X-ray phase and X-ray structural analysis of M(Aet)₂-8H₂O compounds, where M(II) = Sr and Ba; (Aet)^- = (C₁₀H₁₁N₄O₂S₂) is the sulfaethiodole (2-(para-aminobenzene-sulfamido)-5-ethyl-1,3,4-thiadiazole) anion is carried out. Symmetry and unit cell parameters of Sr(Aet)₂•8H₂O and Ba(Aet)₂-8H₂O are found: P2₁/c, Z= 4, a = 10.390(2) ?, b= 14.609(3) ?, c = 21.931(5) ?, β = 92.42(2)°, R = 0.041; and P2₁/c, Z= 4, a = 9.793(2) ?, b = 15.408(4) ?, c = 22.553(6) ?, β = 94.98(2)° respectively. The considered compounds are isostructural. The structure of Sr(Aet)₂-8H₂O is fully studied; the crystals of the compound are composed of the complex centrosymmetric dimeric [(H₂O)5Sr(Aet)₂Sr(OH₂)₅]²⁺ cations, (Aet)^- anions, and water molecules; the independent part of the structural formula of the compound is [Sr(Aet)(OH₂)₅](Aet)•3H₂O. The sulfaethiodole anion is coordinated to the complexing metal atom by oxygen and nitrogen atoms with the formation of a four-membered ring.     

Electroconductivity of Solid Electrolytes in the Systems K3–2x M x PO4 (M = Ca, Sr, Ba)

Solid electrolytes K_{3 – 2x} M _x PO₄ (M = Ca, Sr, Ba) are synthesized and the temperature and concentration dependences of their electroconductivity are studied. Adding calcium and strontium stabilizes the high-temperature -form of K₃PO₄ at room temperature, while barium-containing solid electrolytes undergo an eutectoid decomposition below 430°C. Maximum electroconductivity is exhibited by K_{3 – 2x} Sr _x PO₄ (7.1 × 10^–3 and 1.25 × 10^–1 S cm^–1 at 300 and 700°C).     

Self-assembly and crystal structures of two heteronuclear complexes with [Ag2(μ-dppm)2(MeCN)2](SbF6)2 and [Bu4N]2[M(mnt)3] (M=Mo, W) as components

Two heteronuclear complexes Mo₂Ag₄(μ-dppm)₄(mnt)₆ · 6MeCN (1) and WAg₂(μ-dppm)₂(mnt)₃ · MeCN (2) were synthesized by self-assembly with [Ag₂(μ-dppm)₂(MeCN)₂](SbF₆)₂ and [Bu₄N]₂[Mmnt)₃] (M=Mo or W, dppm=bis(diphenylphosphino)methane, mnt²⁻ = cis-1,2-dicyanoethylene-1,2-dithiolate) as components and characterized by IR spectra, elemental analysis, ¹H NMR spectra, ³¹P NMR spectra and u.v.–vis spectra. The crystal structures of the two complexes were determined by X-ray analysis.     

Eu2+在M3La3(BO3)4(M=Ca,Sr,Ba)中的发光性质

本文研究了Eu²⁺离子在M_yAl_xBO_y+3/2(1+x)(M=Ca,Sr,Ba)基质中的发光性质及磷和卤素对发光的影响。 采用以H₂和N₂混合气体为还原气氛在高温下进行固相反应的方法合成了一系列磷光体。发现,在CaAl_xBO_2.5+3/2x基质中,当X在0.5～2的范围内时及在Sr_yAl₂BO_{4 6+}基质中,当y在2～6的范围时掺入的Eu³⁺不能被H₂还原为Eu²⁺。其他Eu²⁺激活的磷光体一般都产生f～d跃迁的宽带发射,发射峰的波长随着基质组成的不同可在400～600nm的区间的变化。     

Synthesis, structure, and properties of M[VO2(XO4)(H2O)2] · H2O (X = S, M = K, Rb, NH4, Tl; X = Se, M = K, Rb, NH4)

Keeping of MVO(XO₄)₂ under saturated vapor pressure at room temperature resulted in the synthesis of a number of isostructural complexes M[VO₂(XO₄)(H₂O)₂] · H₂O, where X = S, M = K, Rb, NH₄, Tl and X = Se, M = K, Rb, NH₄. The conclusion about the isostructural nature of the synthesized sulfate and selenate compounds was based on X-ray diffraction and vibrational spectroscopy data. Characteristic features of the thermal decomposition of M[VO₂(XO₄)(H₂O)₂] · H₂O on heating in air were identified. It was shown that K[VO₂(SeO₄)(H₂O)₂] · H₂O tends to undergo spontaneous dehydration under ambient conditions to give the monohydrate K[VO₂(SeO₄)(H₂O)].     

四核铁配合物[Fe4(NTB)4(μ2-O)2(μ4-Suc)](ClO4)6促进DNA水解

四核铁配合物[Fe₄(NTB)₄(μ₂-O)₂(μ₄-Suc)](ClO₄)₆与DNA具有较强的结合作用，结合常数k_{b达(5.9±0.4)×10⁵ L·mol^-1。该多核铁配合物由水解途径促进DNA断裂，在酸性及低离子浓度条件下的促进作用较为显著。动力学分析表明DNA水解没有明显的序列选择性，质粒DNA从超螺旋转变为切口形式符合饱和酶动力学规律，饱和速率常数ksat=0.014 min^-1。}     

Exchange interactions in trinuclear multispin complexes [Fe 2III MIIO(p-NitPhCOO)6]?MeCN (M = Co, Ni, p-NitPhCOO- = p-benzoatenitronyl nitroxide radical)

The temperature dependences of the magnetic susceptibilities for the complexes [Fe₂^III M^IIO(p-NitPhCOO)₆]∙MeCN (M = Co, Ni, p-NitPhCOO^–= p-benzoatenitronyl nitroxide radical, MeCN = acetonitrile) revealed the existence of antiferromagnetic exchange coupling among the metal ions in the trinuclear units, as well as between these units and the free radicals in the crystal lattices of the complexes.     

Thiolate-bridged Trinuclear Heterobimetallic Complexes [Cd(μ-SPh-4-Me)4{M(PPh3)2}2] (M?=?Cu, Ag) and [Sn(μ-SPh)6(AgPPh3)2]

Abstract  

Reaction of the [Me₄N]₂[Cd(SPh-4-Me)₄] with two equivalents of [M(PPh₃)₂NO₃] afforded the neutral linear trinuclear complexes [Cd(μ-SPh-4-Me)₄{M(PPh₃)₂}₂] (M = Cu 1, Ag 2) in which two [M(PPh₃)₂]⁺ fragments chelate with the opposite edges of a tetrahedral [Cd(SPh-4-Me)₄]²⁻ moiety via the sulfur atoms of the Me-4-PhS⁻ species. Treatment of [Sn(SPh)₄] with two equivalents of [Ag(PPh₃)₂NO₃] gave the neutral linear trinuclear complex [Sn(μ-SPh)₆(AgPPh₃)₂] (3) that is composed of a central distorted SnS₆ octahedron sharing two opposite planes with two slightly distorted AgS₃P tetrahedrons. Complexes 2 and 3 are air and optically stable. Their nonlinear optical absorption and refraction were investigated under the same conditions. The nonlinear optical absorption and refraction of complex 2 were determined to be α ₂ = 3.11 × 10⁻¹¹ m/W and n ₂ = 4.15 × 10⁻¹² esu, respectively. The nonlinear optical absorption and refraction of complex 3 were determined to be α ₂ = 8.36 × 10⁻¹¹ m/W and n ₂ = 1.47 × 10⁻¹¹ esu, respectively.     

MF2-MgF2(M=Ca,Sr,Ba)体系中钐离子的价态及光谱

高温固相反应合成了钐离子激活的MF_2-MgF_2磷光体,考察了合成条件及基质组成对钐离子价态的影响,并讨论了荧光光谱与基质及钐离子价态间的关系.     

Synthesis and molecular structures of the Co3(μ-OOCPh)4(μ,η2-OOCPh)2[OC(Ph)OHNEt3]2 and Co(Hdmpz)2(OOCPh)2 complexes (Hdmpz = 3,5-dimethylpyrazole)

The product of the thermal reaction between cobalt acetate hydrate and benzoic acid reacts with a triethylamine excess to form the trinuclear complex Co₃(μ-OOCPh)₄(μ,η²-OOCPh)₂[OC(Ph)OHNEt₃]₂, and its reaction with 3,5-dimethylpyrazole yields the mononuclear complex Co(Hdmpz)₂(OOCPh)₂. The compound structures are discussed on the basis of X-ray crystallographic data.     

Complex salts trans-[Rh(β-Pic)4Cl2]X (X = Cl?, ReO 4? , and ClO 4? ): Synthesis, crystal structures, and thermal properties

Three novel complex salts containing the cation trans-[Rh(β-Pic)₄Cl₂]⁺ with the anions Cl⁻ (I), ReO₄⁻ (II), and ClO₄⁻ (III) were obtained and characterized by elemental analysis, X-ray diffraction, NMR spectroscopy, and IR spectroscopy. The complex trans-[Rh(β-Pic)₄Cl₂]ReO₄ crystallizes from DMF as a solvate in which solvent molecules fill the channels formed by the cations and anions. The thermal properties of complexes I, II, and II · DMF were examined by DTA. Final and some intermediate products of the thermolysis were isolated and characterized by physicochemical methods.