La(NO3)3和Pr(NO3)3对高岭石脱羟基动力学的影响

采用热重和微商热重(TG/DTA)综合热分析技术在不同升温速率下研究了掺入La(NO₃)₃和Pr(NO₃)₃的高岭石的热分解过程, 利用Coats-Redfern积分法和Achar微分法对热分析实验数据进行动力学计算, 得到了高岭石脱羟基反应过程中的控制机理函数、 活化能和指前因子等动力学参数; 分析了2种稀土掺入对高岭石脱羟基过程动力学参数的影响, 并用Ozawa法对活化能进行了验证. 结果表明, 未掺稀土和掺入Pr(NO₃)₃的高岭石的脱羟基反应过程均受化学反应模型F₃控制, 反应的活化能分别为307.94和282.86 kJ/mol, 指前因子lnA的值分别为47.8980和44.1718; 掺入La(NO₃)₃的高岭石脱羟基反应过程控制机理函数发生改变, 受化学反应模型F₂控制, 反应活化能为196.02 kJ/mol, 指前因子lnA的值为29.5551. 与未掺稀土的高岭石对比, 掺入Pr(NO₃)₃后活化能和指前因子略有降低; 而掺入La(NO₃)₃后则显著降低, 分别降低了36.34%和38.30%. 采用Ozawa法验证得到的活化能与Coats-Redfern积分法和Achar微分法结果一致.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)-(μ-S)_3(μ-OOCCH_3)(dtp)_3(Py)

<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one.     

The Reaction of Alkenes with Triangulo-Clusters [Pt3(μ-CO)3(PR3)3]

The reactions of the cluster complexes [Pt₃(-CO)₃L₃], where L=PPh₃ 1a, PPh₂Bz 1b and PCy₃ 1c, with activated mono-olefins have been studied under preparative and equilibrium conditions. At low temperature the olefins react quantitatively giving the adducts [Pt₃(-CO)₃L₃(olefin)] (olefin=trans-dicyanoethene, DCE 2a–2c, maleic anhydride, MA 3a–3c). The stereo-chemistry of these unstable clusters has been deduced from low temperature ³¹P, ¹³C, ¹⁹⁵Pt-NMR and I.R. spectra. At higher temperature these adducts in presence of excess of olefin convert quantitatively to stable mononuclear Pt(0) complexes [Pt(CO)L(olefin)] (olefin=DCE 4a–4c, MA 5a–5c, maleimide, MI 6a–6c and 1–4-naphthoquinone, NQ 7a, 7c).     

[(O)MoCu_3(μ_3-S)_3(μ_3-Cl)(PPh_3)_3]·2THF的合成及其晶体结构

固体化合物(NH_4)_6Mo_7O_(24)·4H_2O和(PPh_3)_2CuCl与饱和液体NH_4HS反应获得桔红针状标题晶体。晶体空间群为P2_1/c,晶胞参数a=11.742(2),b=28.186(7),c=19.304(3),β=100.57(2)°,V=6280.4(?)~3,D_c=1.46g/cm~3,Z=4,F(000)=2816。在3≤2θ≤45°范围内收集到8414个独立衍射强度数据,其中3856个I≥1.5σ(I)强度数据参加结构计算。标题化合物分子是以{MoCu_3S_3Cl}类立方烷型簇为核心的分子,Mo—Cu的平均距离为2.716。     

Dy3+在Ba3La(BO3)3 中的光致发光

研究了Ba3La(BO3)3 基质中Dy3 的光致发光特性; 探讨了RE3 的电荷半径比(z/r)和Ce3 , Dy3 含量对Dy3 发光强度及发光颜色的影响; 分析了Ba3La(BO3)3 中Ce3 对Dy3 发光的敏化作用; 确定了Dy3 的 4F9/2→6H15/2及4F9/2→6H13/2跃迁发射的浓度猝灭机制均为电偶极-电四极相互作用.     

簇合物[WOS3Ag3Br(PPh3)3]·(OPPh3)的合成和晶体结构

报道了〖ＷＯＳ３Ａｇ３Ｂｒ（ＰＰｈ３）３〗．（ＯＰＰｈ３）簇合物（Ｃ７２Ｈ６０Ａｇ３ＢｒＯ２Ｓ３Ｐ４Ｗ,Ｍｒ＝１７６４．６１）单晶的合成和结构。该晶体三方晶系,空间各为＄３,晶胞参数,ａ＝１６．１４３（３）,ｃ＝２３．００３（４）Ａ,Ｖ＝５１８９．４（１５）Ａ＾３,μ（ＭｏＫａ）＝３．２９８ｍｍ＾－１,Ｚ＝３,Ｆ（０００（）＝２５９８,Ｄｃ＝１．６９４ｇ／ｃｍ＾３。独立衍射点２１８１,可观察衍射点     

The synthesis and crystal structure of novel Mo-Sn tetranuclear cubane-like cluster [Mo3(SnBr3)(μ3-O)(μ3-S)3(dtp)3(py)3]·(CH2Cl2)

The synthesis and crystal structure of the first example for hybrid Sn-Mo tetranuclear cubane-like cluster compound containing S/O mixed triple capping atom [Mo₃(SnBr₃)(μ ₃-O)(μ ₃-S)₃(dtp)₃(py)₃]·(CH₂Cl₂) (A) (dtp=S₂P(OC₂H₅)₂) are reported. The compound is prepared by the reaction of [Mo₃(μ ₃-O)(μ-S)₃(dtp)₄·(H₂O)] with SnBr ₃ ^? . The molecular structure of the cluster can be described as a [Mo₃OS₃] core with the SnBr ₃ ^? fragment linked to {Mo₃} triangle by three (μ ₃-S). Three Mo-Mo bond lengths are 2.616(2), 2.620(2), 2.628(2) Å, respectively, and the molecule has approximately C_3v symmetry. There is no bonding between Sn and Mo atoms, however, the addition of SnBr ₃ ^? may cause electron transfer from Sn²⁺ to [Mo₃OS₃] core to result in the shortening of Mo-Mo bond distances. The compound crystallizes in the monoclinic space group P2₁/n with refined lattice parameters ofa=13.012(4),b=22.877(6),c=18.585(6) Å,β=96.34(3)°,V=5498(3)ų, andZ=4. Full matrix refinement converged with final agreement factor ofR=0.054,R _w=0.064.     

Synthesis and Structure of [Pd(NH3)4][cis-Pd(NH3)2(SO3)2][Pd(NH3)3(SO3)] · H2O

A new palladium compound [Pd(NH₃)₄][cis-Pd(NH₃)₂(SO₃)₂][Pd(NH₃)₃(SO₃)] · H₂O (I) was synthesized and its structure was studied by X-ray powder diffraction method. In the course of the synthesis, the initial trans-diamminesulfite anionic complex is transformed into the cis-configuration. Further heating in aqueous solution results in isomerization of a substance into a neutral complex [Pd(NH₃)₃(SO₃)]. Crystals I are triclinic: a = 10.3297(2) Å, b = 14.1062(3) Å, c = 6.8531(1) Å, = 101.36(0)°, = 92.74(0)°, = 92.71(0)°, space group P1¯. Structure I consists of the columns with alternating cis-[Pd(NH₃)₂(SO₃)₂]^2– and [Pd(NH₃)₃(SO₃)] complexes and [Pd(NH₃)₄]²⁺ ions between the columns.     

Sm~(3 )在硼酸盐玻璃中的发光及Bi~(3 )对Sm~(3 )的敏化作用

早在六十年代,人们为了寻找较好的激光玻璃,曾对Sm~(3 )离子掺杂的玻璃中的光谱进行过研究。为了探寻新型的激光,发光玻璃,又进一步研究了Sm~(3 )在玻璃中的发光和敏化。我们以寻找一种高亮度,低成本的发光玻璃为目的,研究了基质玻璃组成,敏化离子及其浓度对Sm~(3 )发光性质的影响。 选择B_2O_3-BaO-M_mO_n(M_mO_n=Li_2O,Na_2O,K_2O,MgO,CaO,SrO)玻璃体系,所用原料的纯度皆为分析纯以上,用陶瓷坩埚在1250℃掺杂氧化钐(纯度均大于99％),玻璃的荧光谱和激发光谱,用MPF-4型荧光分光光度计测定。     

Eu(OPri)3/Tb(OPri)3共掺杂P(MMA-co-St)

Eu(OPri)3/Tb(OPri)3共掺杂P(MMA-co-St);Eu(OPri)3/Tb(OPri)3;共掺杂;P(MMA-co-St);荧光性能     

簇合物〔WOS_3 Ag_3 Br(PPh_3)_3〕·(OPPh_3)的合成和晶体结构

报道了〔WOS3Ag3Br(PPh3) 3〕·(OPPh3)簇合物 (C72 H6 0 Ag3BrO2 S3P4W ,Mr=176 4.6 1)单晶的合成和结构。该晶体属于三方晶系 ,空间群为R3 ,晶胞参数 :a =16 .14 0 (3) ,c =2 3 .0 0 3(4) ,V =5 189.4(15 ) 3,μ(MoKα) =3 .2 98mm- 1 ,Z =3 ,F(0 0 0 ) =2 5 98,Dc=1.6 94g/cm3。独立衍射点 2 181,可观察衍射点 195 2 (I≥ 2σ(I) ) ,R =0 .0 496 ,wR =0 .12 48。该晶体由簇合物分子〔WOS3Ag3Br(PPh3) 3〕和以P为中心的扭曲四面体结构的中性分子OPPh3 构成 ,其中的簇合物分子的骨架为由1个W原子、3个S原子、3个Ag原子和 1个Br原子构成的立方烷状。W、O(1)和Br原子位于C3轴上。     

[{(C5Me4R)Ru}3Ru(η3-As3)(μ3,η3-As3)(μ3-As)3], arsenreiche Vierkerncluster

The interaction of [(η⁵-C₅Me₄R)Ru(CO)₂]₂ (1a: R = Me, 1b: R = Et) with yellor arsenic, As₄, affords besides the pentaarsaruthenocenes [(η⁵-As₅)Ru(η⁵-C₅Me₄R)] (2a, 2b) the tetranuclear clusters [{(η⁵-C₅Me₄R)Ru}₃Ru(η³-As₃)(μ₃,η³-As₃)(μ₃-As)₃] (3a, 3b). The structure of 2b and 3b has been elucidated by X-ray analysis.