钙钛矿型催化活性材料结构与性能的研究——La_(k—x)Sr_xCo_(0.75)Me_(0.25)O_(3—δ)体系

用多晶X射线衍射法研究了ABO_3型的[(La_(1-y)Sr_y)_(1-z)□_z][Co_(0.75)Me_(0.25)][○_(3-δ)□_δ]系列化合物的结构和晶格畸变。结构中A位为La~(3+)、Sr~(2+)和约14％的空位随机占有。不同价态的Co离子和Me~(4+)无序地分布于B位。○位为O~(2-)和空位随机占有。A位Sr~(2+)取代La~(3+)量增加,正二价的Co逐渐变为正三价,最后出现正四价。平均晶格畸率<ε_(110)~2>~(1/2),及对CO完全氧化反应的活性迅速增大。因此平均晶格畸变率<ε_(110)~2>~(1/2)可表征钙钛矿相A位的调变作用和与之相关的催化性能。     

Nd_2(Fe_(1-x)Co_x)_(14)B和Y_2(Fe_(1-x)Co_x)_(14)B的磁性

用磁测量和X-射线衍射研究了Nd_2(Fe_(1-x)Cox)_(14)B和Y_2(Fe_(1-x)Cox)_(14)B的晶格结构和内禀磁性。结果表明,低温下当钴含量较少时,Y_2(Fe_(1x)Cox)_(14)B的磁晶格向异性随钴含量的增加而增加,在1.5K和150K温度下,分别在x为0.4和0.2左右时磁晶各向异性常数达到极大;室温时的磁晶各向异性常数却随钴含量的增加而单调下降。用钴代换铁,对Nd_2(Fe_(1-x)Cox)_(14)B的自旋再取向温度的影响是复杂的。1.5K的饱和磁化强度在x=0.1左右达到极大。钴可以显著提高居里温度,对于Nd_2(Fe_(1-x)Cox)_(14)B和Y_2(Fe_(1-x)Cox)_(14)B,钴的作用几乎相同,表明居里温度主要由3d过渡金属原子之间的交换作用决定。     

[Ho_2(phen)_4(H_2O)_4(OH)_2](phen)_2(NO_3)_4的合成、晶体结构及磁性

在甲醇与水的混合溶剂中,经浓硝酸硝化的Ho_2O_3与1,10-邻菲啰啉反应形 成氢氧根桥联的双核钬配合物[Ho_2(phen)_4(H_2O)_4(OH)_2] (phen)_2(NO_3)_4 （phen = 1,10-邻菲啰啉）。单晶X射线衍射晶体结构测定表明晶体属三斜晶系, P1-bar (no. 2)空间群,晶胞参数a = 1.1241(1) nm, b = 1.1439(1) nm, c = 1. 4058 (1) nm, α = 93.989(7)°, β = 98.173(7)°, γ = 108.19(1)°, V = 1.6874(4) nm~3, Z = 1, D_c = 1.737 g/cm~3, F(000) = 880,7752个独立衍射 点中,5702个可观测点满足F_o~2 ≥ 2σ (F_o~2),R_1 = 0.0499, wR_2 = 0. 858。标题配合物由中心对称的双核[Ho_2(phen)_4(H_2O)_4-(OH)_2]~(4+)配阳离 子,邻菲啰啉phen分子及硝酸根NO_3~-阴离子组成。敏个稀土原子与2个邻菲啰啉 配体,2相水分子和2个氢氧根配位形成配位数为8的[HoN_4O_4]四方反棱柱。配位 多面体通过两氢氧根基团形成共棱的[Ho_2N_8O_6]双四方反棱柱[d(Ho-N) = 0. 2549～0.2565 nm, d(Ho-O_(H_2O) = 0.2356, 0.2366 nm, d(Ho-O_(OH)) = 0. 2223, 0.2240 nm]。通过氢键和芳环堆积作用,配阳离子和邻菲啰啉分子排列形成 平行于（10 1-bar）的两维层结构,NO_3~-阴离子位于层之间。标题配合物为顺磁 物质,在5 ～300K区间内遵循Curie-Weiss定律X_m (T + 4.43) = 14.72 cm~3·K ·mol~(-1)(X_m为每摩尔Ho~(3+)离子磁化率）,其Ho~(3+)离子的室温有效磁矩为 10.76 B. M.,与Ho~(3+)自由离子的磁矩基本相同,表明稀土离子间不存在磁交换 作用。     

钴配合物[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4的合成与晶体结构研究

用硫酸钴、4,4'-联吡啶和2-磺酸基乙基膦酸合成了一个新颖的钴化合物:[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4,并对其进行了红外.元素分析、热重测试,通过单晶衍射仪测定了其晶体结构.结果表明,配合物属单斜晶系C2/c空间群,分子式为C_(22)H_(45)Co_2N_4O_(22)PS_2,分子量为930.57,晶胞参数为a=19.8456(18),b=11.2957(10),c=34.719(3)(A),β=106.095(3)°,晶胞体积为7477.9(12)(A)~3,Z=8,Dc=1.653 g/cm~3,F(000)=3856,μ=1.131 mm~(-1),最终残差因子R_1=0.0726,wR_2= 0.1719(相对于5612个I>2σ(I)的可观测衍射点).在这个化合物中,二齿配体4,4'-联吡啶把Co(II)桥连成[Co(4,4'-bipy)]~(2+)链.化合物中的[Co(4,4'-bipy)]~(2+)链有三个不同的朝向.2-磺酸基乙基膦酸没有参与配位而是做为一个有机模板剂填充在[Co(4,4'-bipy)]~(2+)链形成的空隙中.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)_2(μ-Cl)_3[S_2P(OEt)_2]_3

<正> M=1013.98, hexagonal, P63/m, a=b=15.492(2), c=8.530(4)A, γ=120°, V=1773A3, Z=2, Dc=1.899°g.cm-3. Final R=0.042 for 611 reflections.This is a Bl(bicapped) type trinuclear molybdenum cluster with two S capping atoms located on the 63 axis and exhibits full D3h symmetry. The Mo-Mo distances are 2.606(1)A, with a bond order of 11/3. It is paramagnetic.     

α'-(BEDT-TTF)_2C_6H_4(SO_3)_2的合成、结构与导电性

用恒电流电化学结晶法合成了一种新的基于BEDT-TIF的电荷转移盐α'-(BEDT- TIF)_2C_6H_4(SO_3)_2 [BEDT-TIF = 双亚乙基二硫四硫富瓦烯,C_6H_4(SO_3) _2~(2-) = 对苯二磺酸根]。通过四圆X射线衍射方法测定了α'-(BEDT-TTF) _2C_6H_4-(SO_3)_2的结构。晶体属于单斜晶系,P2/n空间群;晶胞参数：a = 0. 77937(17)nm, b = 0.66989(11) nm, c = 3.4422 (7) nm, β = 91.135(12) °, V = 1.7968(6) nm~3。该晶体中BEDT-TTF~+自由基沿a轴方向形成具有二聚体结构 的交错排列型柱状堆积,沿b轴方向由户并户强分子间相互作用形成一维分子链。 电荷补偿阴离子C_6H_4(SO_3)_2~(2-)则在a方向存在较强的作用。沿c轴方向, BEDT-TTF~+自由基层和阴离子层交替排列形成夹心式结构。α'-(BEDT-TTF) _2C_6H_4-(SO_3)_2在ab面的某方向的室温电导率为0.5913 Ω~(-1)·m~(-1),电 阻率-温度测定曲线表明它具有半导体导电行为。在150K附近,晶体发生了某种相 变。     

SYNTHESIS AND STRUCTURE OF (Ph_4P)_2[Ni_3(μ-SC_3H_6S)_4]·2CH_3CN

<正> (Ph4P)2[Ni3(u-SC3H6S)4].2CH3CN was obtained from the reaction of NiCl2.6H2O,Na2(1,2-pdt)(pdtH2=CH3CH(SH)CH2SH) and Ph4PBr.Mr=1361. 80, P21/c,a=10.802(2),b=30.111 (7),c=9. 907(3) A ,B=93. 60(3) ;V= 3216. 0 A3;Z=2,Dc=1. 41g/cm3. The three Ni atoms of the anion are linearly arranged and bridged by four sulfur atoms from the four 1 ,2-propyldithiolato ligands.     

Eu~(3+)掺杂NaBi(MoO_4)_2/TiO_2复合纤维制备及其光裂解水制氢

以电纺TiO_2纳米纤维为基质,利用水热法制备了异质结型Eu~(3+)掺杂NaBi(MoO_4)_2/TiO_2复合纤维。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、 X射线光电子能谱(XPS)、高分辨透射电镜(TEM)、紫外-可见漫反射(UV-Vis DRS)光谱以及荧光(PL)光谱等分析测试手段对样品的物相、形貌和光学性能等进行表征。以三乙醇胺为电子给体,研究了Eu~(3+)掺杂NaBi(MoO_4)_2/TiO_2复合纤维光催化裂解水制氢的反应过程。结果表明:NaBi(MoO_4)_2与TiO_2复合形成异质结,使光生电子-空穴对得到较好分离,而Eu~(3+)掺杂进入NaBi(MoO_4)_2晶格,部分取代Bi~(3+)离子,导致晶胞膨胀,在拓宽光谱响应范围的同时,形成光生载流子的浅势捕获阱,进一步促进了光生电荷的产生、转移,有效提高材料的光催化制氢活性。最佳产氢速率达到7.86 mmol·h~(-1)·g~(-1)。     

CEYSTAL STRUCTURE OF EXTRACTED COMPLEX OF URANYL CHLORIDE WITH DICYCLOHEXYL-18-CROWN-6(MIXED ISOMERS),UO_2Cl_4]_3 [C_(20)H_(36)O_6- (ISOMER A)-H_3O]_4 [C_(20)H_(36)O_6(ISOMER B)-H_3O]_2

<正> Mr= 3584.7, monoclinic, P21/c, a = 14.647(2), b = 20.333(2), c = 25.759(3) A, β= 91.05(1)°, Z = 2, V = 7670.1 A3, Dc = 1.544 g/cm3,μ=32.629 cm-1, R=0.056 for 4207 observed reflections. Each asymmetric unit consists of two UO2Cl42- complex anions and three C20B36O6-H3O+ complex cations. In two of the complex cations (isosaer A), HaO+ cation is anchored in each crown ether ring by three stronger hydrogen bonds. In another complex cation (isomer B) only two stronger hydronger bonds are formed between the H3O+ cation and crown ether. The third hydrogen bond is very weak.     

Alternating Double Trinucleate [Yb_3(μ_3-OH)_2O]_2 Chain Bridged by μ_3-OH Mode in a 3D Yb~(3+)-CP and Its Near Infrared Luminescent Properties

A new 3D coordination polymer,namely,[Yb_3(μ_3-OH)_3(μ_2-OH)(DDLA)_(2.5)(BIPY)](1,H_2DDLA = 2,2-dipyridyl-4,4-dicarboxylic acid,BIPY = 2,2?-bipyridine),has been synthesized via solvothermal method. The complex crystallizes in triclinic,space group P1 with a = 7.7339(4),b = 15.6699(8),c = 17.2221(9) ?,α = 68.8630(10),β = 88.1890(10),γ = 88.1740(10)°,V = 1945.27(17) ?~3,Z = 2,D_c = 2.296 g·cm~3,μ(MoKα) = 1.075 mm~(-1),F(000) = 1268,S = 1.068,R = 0.0263 and wR = 1.067 for 5176 observed reflections with I 2σ(I). Compound 1 contains a unique alternating double trinucleate {[Yb_3(μ_3-OH)_2OH]_2}_n chain,in which Yb~(3+) is bridged through μ_3-OH and μ_2-OH two coordination modes. The alternating double trinucleate chains are further extended into a 3D structure through DDLA~(2-) ligands by different coordination modes. The photoluminescence spectra show 1 is highly sensitized by the characteristic emission of Yb~(3+) in the NIR region.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_2[S_2P(OEt)_2]_3][SOP(OEt)_2](0)_2

<正> M=1140.85, monoclinic, P21/c. a=12.748(2), b=14.320(2), c=23.118 (3)A,β=101.07(1)°, V=4141(2)A3, Z=4, Dc=1.830 g.cm-3. Final R=0.039 for 4160 reflections.The title compound is a rather irregular trinuclear molybdenum cluster having only two M-M bonds with two shorter Mo-Mo distances of 2.808(1), 2.839(1), and one longer Mo-Mo distance of 3.337(1)8. The existence of two Mo-Mo bonds is coincident with the electron counting for {Mo3} cluster core, and may be regarded as a result of the oxidation of a compound Mo3(μ3-S)(μ-S)2 (μ-L)[S2P(OEt)2]4(L') (L'=neutral ligands)1 characterized by us previously.     

STRUCTURE OF (C_5H_7S_2) [Mo_3(μ_3-0) (μ-X)_3(μ-OAc)_3C1_3] (X=Cl,Br)

<正> Introduction. In order to synthesize trinuclear Mo cluster compounds with three bridge-linked acetoxyle groups, we changed the reaction condition described in reference(1) thus obtaining two new cluster compounds with the formula(C_5H_7S_2)[Mo_3(μ_3-O)(μ-X)_3(μ-OAc)_3Cl_3] (referred to beIow as compound (Ⅰ) when X=C1 and compound (Ⅱ) when X=Br). The diffraction work shows that the crystals of these two compounds are isomorphic.     

CRYSTAL AND MOLECULAR STRUCTURE OF β-(Et_4N)_3 [Fe_3(SPh)_3Br_3C1_3]

<正> Introduction. Previously, we have reported the compound α-(Et_4N)_3[Fe_3(SPh)_3-Br_3Cl_3](Ⅰ)~1 with C_2 symmetry. An isomer(Ⅱ) of this compound, which has D_3dsymmetry, is reported in this paper. Brow-green crystals of Ⅱ is obtained from the reaction of FeCl_2, PhSNa and Et_4NBr (1:1:1) in acetonitrile solution.     

稀土氨基酸配合物的研究(Ⅲ)——[Pr_2Cl_2(Gly)_4(H_2O)_6]·4Cl配合物的晶体结构

在水溶液中合成并培养了甘氨酸镨(或钐)配合物单晶,元素分析结果表明,化学式可用Ln(Gly)_2·Cl_3·3H_2O表示(Ln=Pr,Sm;Gly为甘氨酸)。X射线衍射测定结果,其结构式为(Pr_2Cl_2(Gly)_4(H_2O)_6]·4Cl,属单斜晶系,空间群P2_1/n,Z=2,晶胞参数为:a=1.0055(2),b=1.4619(3),c=1.0041(2)nm,β=102.09(1)°。每两个中心Pr~(3+)由两个甘氨酸羧基桥联成双核配合物。Pr~(3+)还与一个甘氨酸羧基双齿配位,再与3个O(H_2O)和一个Cl配位。Pr~(3+)的配位数为8。配位多面体由两个三角十二面体组成。     

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(C_(14)H_9O_3)_2(C_(12)H_8N_2)_2(NO_3)

A new europium(III)complex Eu(C_(14)H_9O_3)_2(C_(12)H_8N_2)_2(NO_3)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_1/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D_c=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm~(-1),F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1(594 nm)and ~5D_0→~7F_2(618 nm).In addition,its X_(m )T decreases from 1.29767 cm~3?mol~(-1)?K at 300 K to 0.01531 cm~3?mol~(-1)?K at 2 K.     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER (η~5-C_5H_5)_2W_2Fe_2(μ_3-S)_2(CO)_8

<正> (η5-C5H5)W2Fe2(μ3-S)2(CO)8,Mr = 897. 80,monoclinic,C2/c,a= 18. 019 (2),b = 8. 330(1),c= 16. 043(2) A ,β= 114. 30(1)°,v = 2194. 7(6)A3,z= 4, Dx = 2. 717g/cm3, A(MoKa) = 0. 71037 A , μ= 122. 01cm-1, F (000) = 1656, T = 295K,R=0.056,Rw = 0. 059 for 1250 observed reflections. The crystals of the title compound are isomorphous with the analog (η5-C5H5)2Mo2Fe2(μ3-S)2(CO)8.     

STRUCTURE OF TRISUBSTITUTED TUNGSTOSILICATE ANION [A-β-SiW_9Al_3(H_2O)_2O_36(μ_3-O2/2)]_2~14-

<正> Crystal of H14C[A-β-SiW9Al3(H2O)2O36(μ3-O2/2)]2 ·8H2O belongs to monoclinic system, space group P2/m. with a= 1 7. 525(6), b=14.348(3). c= 21. 669(8) A , β=113. 12(8)°, V = 5011 (3) A3,Z = 2. Dc = 3. 254 g. cm-3, A (MoKα) = 0. 70169 A , μ=223. 21 cm-1, F(000) = 4614, T = 298K. R=0. 066 for 3010 unique reflections [I≥5σ(I) ]. The crystal consists of water molecules, protons (or H3O+ ) and dimeric anions [A-β-SiW9Al3 (H2O)2O36(μ3-O2/2)D214.the half of which has a SiO1 tetrahedron in the center, a W3O13 group, two W2Al(H2O) O12 groups and a W2AlO13 group around the SiO4.     

[Al_3Nd_6(μ_2-Cl)_6(μ_3-Cl)_6(μ_2-Et)_9Et_5OPr~i]_2的单晶结构

从均相Ziegler-Natta催化剂分离出有催化聚合活性的[Al_3Nd_6(μ_2-Cl)_6(μ_3-Cl)_6(μ_2-Et)_9Et_5OPr~i)_2单晶,并用X光衍射法测得其晶体结构.结果表明,该单晶是由多核Nd-Al双金属配合物的二聚体组成,属三斜晶系;晶体的空间群为PI.晶胞参数α=15.196(6),b=15.263(5),c=13.749(4)A;α=90.01(2),β=95.12(3),γ=82.65(3)°;V=3149.5A~3;Z=1.Nd原子的配位数是7,构型为单帽三棱柱.Nd原子由三重和二重氯桥连成分子骨架.本文对双金属配合物的催化活性中心也进行了讨论.     

CRYSTAL STRUCTURE OF MIXED-METAL CLUSTER(η~5-C_5H_5)_2Mo_2Fe_2(μ3-S)_2(μ-CO)_2(CO)_6

<正> Mr= 721.98,monoclinic, P21/n,a= 9.773(1), b = 6.641(3), c = 16.258(1)A,β=92.25(1)°,V=1054.4(7)A3,Dx = 2.274g/cm3,Z=2,λ(MoKα)=0.7107A.Final R= 0.024,Rw= 0.036 for 1554 observed reflections. The cluster core Fe2Mo2 is a rhombic plane with Mo-No distance of 2.827A and average Mo-Fe distance of 2.773A.     

硫氰酸根络合物的晶体化学——Ⅰ.Cu(NH_3)_2Ag(SCN)_3的晶体结构

Cu(NH_3)_2Ag(SCN)_3是深绿色六方柱状(或六方双锥)晶体.通过X射线研究确定晶体的空间群为?;共晶胞参数为:a=9.22?,c=7.38?;晶胞内含有两个{Cu(NH_3)_2Ag(SCN)_3)(ρ_(obs)=2.308克/厘米~3,ρ_(ealc)=2.319克/厘米~3).晶体的结构是通过Patterson函数投影P_0(u,v),P_0(u,w)和电子密度投影ρ_0(x,z)的计算进行测定的.在这个晶体结构中,Ag原子由6个S原子按八面体型配位方式直接配位;每两个AgS_6八面体通过由三个S原子所组成的共面互相衔接,沿着c轴无限延伸.SCN的另一端N原子与cu原子形成正三角型配位,CuN_3上下又排布着两个NH_3分子,使Cu具有三方双锥的配位构型.这样,SCN利用其两端原子把Ag与Cu联系起来,使晶体具有三维骨架型的结构.