Crystal structure and properties of terbium o-methylbenzoate complex with 1,10-phenanthroline [Tb（o-CH3C6H4COO）3（C12H8N2）]2

A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen (where o-MBA =o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solution and its crystal structure was deter-mined by X-ray diffraction. The crystal of the complex Tb(o-MBA)_3phen belongs to triclinic crystal system and P 1 (#2)space group. The crystal data are as follows: a=1.4371(4)nm, b=1.7387(2)nm, c=1.3109(2)nm, α=96.37(1)°,β=107.21(2)°, γ=82.78(2)°, V=3.094(1)nm~3, Z=2, M_r=1489.12, D_c=1.598g·cm, μ=2.330mm~(-1) and F(000)=1488.00.The final R and R_w are 0.038 and 0.047 for 8668Π>2σ(Ⅰ)] unique reflections, respectively. In the complex each Tb~(3 ) ion iseight-coordinated by one 1,10-phenanthroline molecule, one bidentate carboxytate group and four bridging carboxylategroups. The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and the bridging biden-tate. Excitation and luminescence data observed at room temperature show that the title complex emits     

溶液配位化学研究:Ⅸ.Pt(Ⅱ)-Phen-PCA体系

用pH电位滴定法测定了含1,10-邻菲咯啉(Phen)和羧酸(CA)配体的三元混配配合物Pt(Phen)(CA)+体系的稳定常数,比较和讨论了各种三元混配配合物之间的稳定性差异.实验结果表明:在三元混配配合物Pt(Phen)(PCA)+中(PCA为苯基羧酸)存在分子内芳环堆积作用,堆积程度依赖于苯基和配位的羧酸根之间的亚甲基数目,其中以2-苯乙酸和3-苯丙酸与邻菲咯啉为最佳堆积.     

溶液配位化学研究：Ⅺ.Pt（Ⅱ）—Phen—PCA体系

用pH电位滴定法测定了含1，10-邻菲咯啉（Phen)和羧酸（CA）配体的三元混配配合物Pt(Phen)(CA)^ 体系的稳定常数，比较和讨论了各种三元混配配合物之间的稳定性差异，实验结果表明：在三元混配配合物Pt(Phen)(PCA)^ 中（PCA为苯基羧酸）存在分子内芳环堆积作用，堆积程度依赖于苯基和配位的羧酸根之间的亚甲基数目，其中以2-苯乙酸和3-苯丙酸与邻菲洛啉为最佳堆积。     

水杨酸锰的热分解机理及纳米氧化锰形貌

用流变相-前驱物反应法合成了水杨酸锰配合物.通过元素分析和TG分析确定该配合物的组成为Mn(HSal)2·2.5 H2O(HSal=o-OHC6H4COO);XRD确定该配合物为单斜晶系,晶胞参数为α=1.893 5(4)nm,b=0.617 9(0)nm,c=1.732 5(6)nm,β=114.93(1)°,V=1.838 2(3)nm3,Z=6,ρcal=1.775 kg/dm3,ρexp=1.769 kg/dm3;IR研究表明配合物中羧酸根与Mn2 以双齿螯合方式配位.样品在氮气中经330℃热分解的最终产物是MnO和有机化合物,在空气中经800℃热分解的最终产物为Mn3O4.TEM观察表明,MnO和Mn3O4均为球形粒子,平均粒径分别约为25和28 nm;激光粒度分析仪测定MnO和Mn3O4的平均粒径约为45.6和69.1 nm.     

溶液配位化学研究:IX.Pt(Ⅱ)-Phen-PCA体系

用pH电位滴定法测定了含 1 ,1 0 -邻菲咯啉 (Phen )和羧酸 (CA )配体的三元混配配合物Pt(Phen) (CA ) +体系的稳定常数 ,比较和讨论了各种三元混配配合物之间的稳定性差异。实验结果表明 :在三元混配配合物Pt(Phen) (PCA) +中 (PCA为苯基羧酸 )存在分子内芳环堆积作用 ,堆积程度依赖于苯基和配位的羧酸根之间的亚甲基数目 ,其中以 2 -苯乙酸和 3-苯丙酸与邻菲咯啉为最佳堆积。     

两种新型铱(Ⅲ)配合物的合成与性质研究

分别以2-苯基吡啶(ppy)为第一配体,以1-苯基-1,3-丁二酮(phbd),1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5(pmbp)为第二配体合成了两个新的铱配合物Ir(ppy)2(pmbp)、Ir(ppy)2(phbd),通过红外光谱、元素分析和核磁共振对其化学组成进行了结构表征,表征结果与理论吻合良好;配合物在紫外吸收光谱图上的290~310 nm处出现了强的配体自旋允许的单重态π-π*跃迁吸收峰,在400~460 nm处出现了配合物分子内金属铱到配体的单重态和三重态电荷跃迁吸收峰(1MLCT和3MLCT);同时配合物Ir(ppy)2(pmbp)、Ir(ppy)2(phbd)在荧光光谱上522、518 nm处出现了强的绿光发射。     

铅离子-苯甲羟肟酸配合物捕收剂(Pb-BHA)的单晶结构分析

铅离子-苯甲羟肟酸配合物捕收剂(Pb-BHA)在钨矿、锡石和钛铁矿等氧化矿浮选中展现出良好的浮选性能和应用前景,但其精确分子结构尚不清楚,阻碍了配合物浮选作用机理的深入认识和金属基捕收剂分子设计的开展。本文培养了铅离子与BHA摩尔比分别为1∶1和2∶1的两种Pb-BHA配合物单晶(配合物1和配合物2),并采用X射线结构分析方法对其结构进行解析,包括配合物晶体结构、分子结构、空间堆积结构、分子间相互作用等。结果表明：配合物1的分子式为Pb₆L₈(NO₃)₄ (HL=BHA),配合物2的分子式为[Pb₆L₈(NO₃)₃]NO₃,铅离子与配体氧原子配位形成非平面“O,O”五元环螯合物构型,铅离子配位数为五配位、六配位和七配位。配合物分子通过Pb—O键与临近配合物相键接形成具有单体重复结构的三维扩展堆积聚合物。配合物中弱相互作用以O···H、H···H、Pb···O为主,π-π相互作用在分子间相互作...     

XPS和AES研究铜表面PMTA防变色膜

本工作对比了各种防铜变色剂的防变色效果,结果表明,1-苯基-5-巯基四氮唑(PMTA)的防变色效果优于化学钝化、电解钝化、苯骈三氮唑(BTA)、羟基苯骈三氮唑(HBT)、2-巯基苯骈噻唑(MBT)。用PMTA处理铜的最佳条件为:PMTA1～1.2g/L,pH=5,20～40℃,4min。XPS和AES分析表明,PMTA在Cu_2O上形成配合物膜,膜中铜为+1价。PMTA分子中的N、S均参与配位。从膜的AES元素深度分布曲线的恒组成区求得的配合物膜组成(A.C.％)为:Cu 40.9,C 32.3,N 16.2,O 7.9,S 2.9。     

一个新铂配合物的合成、表征及反应机理的研究

合成了新配合物：氯化二氯二(1-二氯甲基-2-二甲基锍乙基甲基硫醚)合铂(Ⅱ)。通过元素分析及IR、^1H-NMR、^13C-NMR、H-HCOSY和MS分析进行了结构表征。根据产物结构推测反应机理为：氯化-3,3-二氯-二烯丙基锍在室温和乙醇钠作用下,首先发生分子间的分解、加成反应,生成一个新的硫醚,该硫醚再与铂配位,形成新的铂配合物。     

铕-邻菲咯啉衍生物-脂肪酸配合物的合成及性能

合成2-苯基咪唑并[5,6-f]邻菲咯啉(PIP),2-(4-苯酚)咪唑并[5,6-f]邻菲咯啉(pHPIP),2-(4-甲氧基苯摹)咪唑并[5,6-f]邻菲咯啉(pMPIP)和2-(4-甲酰基苯基)咪唑并[5,6-f]邻菲咯啉(pAPIP)等4种邻菲咯啉衍生物,并分别以其为第一配体,选择丁酸(BAH),正庚酸(HAH)和十四酸(TAH)为第二体合成12种新的铕.邻菲咯啉衍生物-脂肪酸荧光配合物.通过EDTA配位滴定分析、元素分析、红外光谱、紫外可见光谱和热分析对配合物的组成、结构进行表征,并研究其热稳定性能;采用荧光光谱分析研究其发光性能.结果表明,目标配合物比其对应的二元配合物的荧光强度大大提高,说明第二配体脂肪酸和第一配体之间产生很好的协同效应;该类配合物有较好的热稳定性,可成为很好的光致发红光和电致发红光材料.     

A novel process for copper protection in the simulated industrial cooling water based on click synthesis and self‐assembling method

The triazole inhibitor of 1‐(p‐tolylthio)‐1H‐1,2,3‐triazole‐4‐carboxylic acid (TTC) was synthesized via the Cu(I)‐catalyzed azide‐alkyne 1,3‐dipolar cycloaddition reaction. The self‐assembling method was performed to fabricate the self‐assembled film of TTC on the copper surface. The electrochemical measurement results indicate that the TTC film can efficiently protect the copper from corrosion in high concentrated industrial cooling water. The protection efficiency of TTC film for copper is 92.2%. Surface characterizations imply that the copper with TTC film after corrosion is covered with multiple protective layers. It probably contains Cu(I) and Cu(II) complexes mixed with nitrogenous compound, Cl^? and SO₄^2?. The result of quantum chemical calculation shows that the superior performance of TTC film is related to the adsorption of TTC molecules on copper surface horizontally. This kind of adsorption is mainly achieved via the adsorption centers of triazole ring and O atoms in TTC molecule.     

TC4／Ag-Cu—Ti／1Cr18Ni9Ti钎焊接头界面组织与结构

以Ag—Cu—Ti箔状钎料对钛合金TCA和不锈钢1Cr18Ni9Ti进行了真空钎焊。采用扫描电镜、能谱分析、金相显微镜和x一射线衍射等分析测试手段对钎焊过程中所形成的反应产物和接头界面结构进行了分析。结果表明：接头界面形成了Ti（s．s）、AS（s．s）、Ti—Cu金属问化合物等反应产物。连接温度较低（920℃）时,界面结构依次为1Cr18Ni9Ti／TiCu／Ag（s．s）＋少量Ti2cu／％2cu／Ti2cu＋Ti（s．s）／TC4;连接温度升高（960oC）时,界面结构为1Crl8Ni9Ti／Ti：Cu／Ti：Cu＋矩（s．s）／Ti2Cu／Ti2Cu＋Ti（s．s）／TCA;连接温度较高（1000oC）时,界面结构为1Crl8Ni9Ti／TiCu2／TiCu／Ti2Cu／Ti：Cu＋Ti（s．s）／TC4。提高钎焊温度与延长保温时间对钎焊接头界面组织结构有相似的影响,各反应相、反应层逐渐长大,金属问化合物反应相所占比例增大,而Ag（s．s）组织所占的比例变得更小,这种趋势随着焊接工艺参数的提高更加明显。     

Synthesis and Structure of Tetrapyridine Diperrhenate Zinc(II) Complex pyZn(OReO)2

The crystal structure of the title complexes described as py4Zn(OReO3)2 was synthesized and determined by single-crystal X-ray structure analysis and the comparison was made to Zn(ReO4)24H2O. The crystal of is monoclinic with space group P21/c. It has the following parameters: =1.0325(1) nm, =1.4693(1) nm, c=1.6837(1) nm, 99.187(2)? V=2.5215(3) nm3, Z=4, dc=2.324 g/cm3 and Rf=0.067, Rw=0.089. The structure consists of two almost tetrahedral ReO units and a slightly distorted ZnN4O2 octahedron formed by four N atoms from four pyridines and two O atoms belonging to two perrhenates in which Zn is central.     

铜偏聚区的高分辨电镜分析

研究铜在钢中的时效强化和沉淀规律具有理论意义和实用价值。应用JEM-2010高分辨电镜研究了Fe-1．18Cu、Fe-1．55Cu高纯钢在时效时组织结构的变化规律,发现,含铜高纯钢固溶处理后,在550℃、650℃时效过程中,首先在铁素体晶粒中析出含铜偏聚区,铜原子偏聚在（001）α晶面上。在时效峰处为富铜的G、P区颗粒,其直径为4—20nm,呈层状的圆饼状,一般5—9层,富铜层和贫铜层相间分布,每一层厚度约为1—2nm。G、P区与铁素体基体半共格。G．P区的富铜区内及周边存在高密度位错和层错。在过时效初期,含铜偏聚区颗粒长大,偏聚区内富铜层和贫铜层的数量增多,富铜层厚度减小,位错密度降低。在铁素体基体上弥散分布的G．P区是含铜高纯钢时效强化的原因。     

Standard energies of combustion and standard enthalpies of formation for the complexes RE （Et2dtc）3（phen） （RE = Ho, Er, Tm, Yb, Lu）

The treatment of RECl3.xH2O （RE = Ho, Er, Tm, Yb, Lu; x = 3-4） with sodium diethyldithiocarbamate （NaEtEdtc-3H2O） and 1,10-phenanthroline hydrate （o-phen.H2O） in absolute ethanol yielded five ternary solid complexes RE（EtEdtC）a（phen）. IR spectra of the complexes showed that RE^3＋ coordinated to two sulfur atoms in NaEt2dtc and two nitrogen atoms in o-phen. The constant-volume energies of combustion of the complexes have been determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion and standard enthalpies of formation were calculated.     

Study on syntheses and structures of nine-coordinated mononuclear K[TbⅢ(edta)(H2O)3]·5H2O and binuclear K4[TbⅢ2(Httha)2]·14H2O complexes

The crystal and molecular structures of the K[TbⅢ(edta)(H2O)3]-5H2O (edta = ethylenediaminetetraacetic acid) and K4[TbⅢ2(Httha)2]+14H2O (ttha = triethylenetetraminehexaacetic acid) complexes have been determined by sin-gle-crystal X-ray diffraction analyses. The crystal of the K[TbⅢ(edta)(H2O)3]·5H2O complex belongs to orthorhombic crys-tal system and Fdd2 space group. The crystal data are as follows: a = 1.9373(5) nm, b = 3.5429(10) nm, c = 1.2114(3) nm, V = 8.315(4) nm3, Z= 16, M = 630.35, Dc = 2.014 g cn-3, m = 3.683 mm-1 and F(000) = 5024. The final R and wR values are 0.0224 and 0.0557 for 3189 [I> 2.0o(I)] unique reflections, and 0.0245 and 0.0567 for all 8206 reflections, respectively. The [TbⅢ(edta)(H2O)3]- complex anion has a nine-coordinated pseudo-monocapped square antiprismatic structure in which the nine coordinate atoms, two N and seven O come from one edta ligand and three water molecules. The crystal of the K4[TbⅢ2(Httha)2]·14H2O complex belongs to monoclinic system and P2(1)/n sp     

Crystal Structures of Dy_2(WO_4)_3 and GdY(WO_4)_3

Two compounds, Dy2(WO4)3 and GdY(WO4)3, were synthesized by using the standard solid state reaction technique. The crystal structure was determined by powder X-ray diffraction and Rietveld refinement method. It is found that both compounds have Eu2(WO4)3-type monoclinic structure, with space group C 2/c, Z = 4. The unit cell parameters of Dy2(WO4)3 are a = 0.75981(1) nm. b = 1.13220( 1) nm, c = 1.13254( 1) nm, and β= 109.8001(3)°, and those of GdY(WO4)3 are a = 0.76175(1) nm, b = 1.13543(1) nm, c = 1.13496(2) nm, and bbbbbbbbbβwhile each rare-earth atom is surrounded by eight oxygen atoms. WO4 tetrahedra share their four vertices with REO8 (RE = Dy, Gd, or Y) trigondodecahedra and some REO8 trigondodecahedra share an edge with each other. The phase transition and the magnetic properties were investigated by differential thermal analysis (DTA) and dc superconducting quantum interference device (SQUID) magnetometer.     

机械合金化制备铜碳过饱和固溶体

采用机械合金化方法制备Cu-4wt%C过饱和固溶体,通过SEM和XRD分析研究了机械合金化中Cu-C复合粉末的形貌变化及碳在铜中的固溶度扩展问题.结果表明,机械合金化过程中Cu粉和C粉形成了层状复合粉末;随着球磨时间的增加,C的衍射峰逐渐消失,Cu的衍射峰逐渐宽化,并且位置发生偏移;球磨24h后,C原子固溶到Cu中,Cu的点阵常数达到0.3620nm,晶格膨胀了0.15%.     

Synthesis, crystal structure and properties of two ternary rare earth complexes with aromatic acid and 1,10-phenanthroline

Two dimeric rare-earth complexes [Eu(o-MOBA)₃phen]₂·2H₂O (1), [Tb(o-MOBA)₃phen]₂·2H₂O (2), (where o-MOBA = o-methoxybenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. Both of them consist of neutral dimeric molecules, crystallize in triclinic system, space group P. Each RE(III) ion is nine-coordinated with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate group, two bidentate bridging carboxylate groups and two tridentate bridging carboxylate groups. Complex 1 shows bright red luminescence, 2 shows green luminescence under UV light at room temperature, respectively. The thermal analysis indicates that they are all quite stable to heat.