γ辐照诱导金纳米粒子的形成和形貌重塑

在十六烷基三甲基溴化铵(CTAB)水溶液中，抗坏血酸(AA)将橙黄色的Au³⁺还原为无色的Au⁺,在γ射线产生的水合电子的作用下，Au⁺进一步还被原成Au⁰，并在微量的Ag⁺诱导所产生的CTAB胶束中生长成为Au纳米棒。控制γ辐照的时间，可以实现金纳米粒子的形貌重塑，即由最初的棒状变为立方体，最终变为多面体。     

一种新的三维超分子化合物[Ni(H2O)6(fum)]·2(hmt)·4H2O的合成和晶体结构(fum=反丁烯二酸根；hmt=六次甲基四胺)

The synthesis of nickel supramolecular compound with hexamethylenetetramine and fumarate ligands is reported. The compound [Ni(H₂O)₆(fum)]·2(hmt)·4H₂O (1) (fum=fumarate; hmt=hexamethylenetetramine) were characterized by elemental analysis, crystal structure, IR. Compound 1 crystallizes in the triclinic system, space group P1, and with Z=1. Cell parameters: a=0. 934 6(1), b=0.933 8(1), c=0.938 8(2) nm, α=79.46(1)°, β=77.84(1)°, γ=61.29 6(7)°. Every metal ion has a octahedral coordination geometry formed by six oxygen atoms from six water molecules, and the relative independent components [Ni(H₂O)₆]²⁺, fumarate anions, hmt and H₂O molecules are linked together by two kinds of hydrogen bonds (O-H…O, and O-H…N) to form a three-dimensional structure. CCDC: 256355.     

Synthesis andCrystal Structure of{[Mn（H2O）4（3,3′—azpy）]（3,3′—azpy）3（PF6）2}n

The complex {[Mn(H2O)4(3, 3?-azpy)](3, 3?-azpy)3(PF6)2}n (3, 3?-azpy = 3, 3?- azobispyridine) has been synthesized and characterized. The crystal (C40H40F12MnN16O4P2, Mr = 1153.76) belongs to the triclinic system, space group P ī with the following crystallographic parameters: a = 10.761(2), b = 11.040(2), c = 23.365(4) ?, ( = 85.52(1), ( = 82.69(1), ( = 70.44(1)°, V = 2592.5(8) ?3, Dc = 1.478 g/cm3, ((MoK() = 4.16 cm-1, F(000) = 1174, Z = 2, final R = 0.0493 and wR = 0.1158 for the observed reflections (I > 2.00((I)). The X-ray analysis revealed that manganese(Ⅱ) cation coordination environment is a distorted octahedral geometry, and the Mn2+ cation is coordinated by four oxygen atoms of water in the equatorial plane, while the two nitrogen atoms of 3, 3?-azpy occupy the axial positions. The complex forms a one-dimensional chain structure via 3, 3?-azpy bridging ligand.     

轴向配体的碱性对Co(SBMe)双氧加合物和Cu(SBPh)结构影响的ESR研究

用希夫碱钴（Ⅱ）和铜（Ⅱ）配合物作为模型化合物，系统地研究了轴向配体的碱性对模型化合物ＥＳＲ参数的影响。实验发现，钴（Ⅱ）配合物的│Ａ│张量随轴向配体碱性的增加而减小，而铜（Ⅱ）配合物的│Ａ│张量正好相反。用π反馈作用解释了这一现象。     

气液色谱法研究双-(O,O′-二正辛基二硫代磷酸酯)合镍(Ⅱ)与伯醇加合反应的热力学性质

本文用气液色谱法研究了 Ni[(C_8H_(17)O)_2PS_2]_2与 C_1—C_4伯醇加合反应的热力学性质.测定了317—353K 范围内加合反应的平衡常数,用作图法求得反应的ΔH和ΔS.ΔH、ΔS 与伯醇的碳原子数之间呈线性关系:-ΔH=11.8+4.57X (kJ/mol)-ΔS=30.6+16.4X (J/mol·K)用静电作用模型描述了加合物成键的实质.加合反应的平衡常数可以用经验公式描述:lgK=-1.601-0.8572X+(619.1-237.8X)/T     

BaWO4纳米线束的合成及其光学性质研究

High quality BaWO₄ nanowire bundles have been synthesized in toluene-sodium dodecylbenzene sulphonate (SDBS)-small amount PEG20000-H₂O reverse micelle system. XRD result shows that the obtained BaWO₄ belongs to tetragonal phase with scheelite structure. TEM results demonstrate that the obtained BaWO₄ nanowire bundles have high aspect-ratio (>650). The experimental results confirm that PEG20000 plays a key role for the formation of BaWO₄ nanowire bundles. Other factors which influence the morphology and crystallinity of the product are also briefly discussed. Moreover， the obtained BaWO₄ nanowire bundles exhibit strong photoluminescence centered at 397.3 nm with λ_ex=343.5 nm at room temperature， which is different from the bulk BaWO₄ crystals.     

双核铜配合物{Cu[μ-S2P(C2H5O)2](C10H8N2)}2的合成和晶体结构

Binuclear Copper (Ⅰ) Complex {Cu[μ-S₂P(C₂H₅O)₂](C₁₀H₈N₂)}₂ was synthesized and characterized by elemental analysis, IRand X-ray diffraction analysis.The crystal belongs to triclinic system, space group P1 with Z = 1, cell dimentions are a = 1.0613 (5), b = 1.0723 (3), c = 0.9397 (2) um, a = 111.11 (4), β = 115.57(6), γ = 85.28(2)°, V= 0.8583(6) nm³.The structure was refined to R = 0.039 and Rw = 0.042 for 2527 reflection with Ⅰ≥3σ(Ⅰ).The complex exists as a centrosymmetric dimer with a Cu-S-P-S-Cu-S-P-Schair eight-membered ring in which Cu atoms are bridged by di-μ-S-P-Sgroups.     

含茂基、烷氧墓及乙酰氧基混合配位镧系金属有机化合物的合成及表征

本文通过二茂基镧系金属氯化物Ｃｐ２ＬｎＣｌ（ＣＰ＝Ｃ５Ｈ５；Ｌｎ＝Ｄｙ，Ｈｏ，Ｙｂ）与等摩尔的ＮａＯＡｃ（Ａｃ＝ＣＨ３ＣＯ）及烷基醇ＨＯＲ（Ｒ＝－ＣＨ２ＣＨ２ＣＨ３，－ＣＨ２ＣＨ＝ＣＨ２）在四氢呋喃溶剂中混合一步反应，合成了六种新的含三种不同配位基的镧系金属有机化合物。化合物的元素分析结果符合通式ＣｐＬｎ（ＯＲ）（ＯＡｃ），红外光谱显示了η＾５－Ｃｐ、ＯＲ及ＯＡｃ基团的特征吸收峰，质谱显示了化合物     

新颖无限三股螺旋钴配位聚合物{[Co(4,4′-bipyridine)(4,4′-azobispyridine)2(NCS)2]·H2O}n的合成、结构和性质的研究

The novel complex {[Co(bipy)(azpy)₂(NCS)₂]·H₂O}_n (where bipy=4,4′-bipyridine, azpy=4,4′-azobisp- yridine) has been synthesized and characterized by elemental analyses, IR, UV, thermal analyses, and vari-able-temperature magnetic susceptibility. The crystal (C₃₂H₂₆CoN₁₂OS₂, M_r=717.70) belongs to the orthorhombic, space group Pnna, a=2.21312(16)nm, b=1.40403(10)nm, c=1.14237(8)nm, V=3.5497(4)nm³, Z=4, D_c=1.343g·cm^-3, μ=0.645mm^-1, F(000)=1476, and final R₁=0.0691, wR₂=0.1129 for 231 parameters and 1674 observed reflections [I >2.00σ(I)]. The Co(Ⅱ) atom is, in a distorted octahedral geometry, coordi-nated by six nitrogen atoms from two bridging bipy, two monodentate azpy, and two thiocyanate groups. The bridging ligand bipy links Co(Ⅱ) atoms to form the infinite “rod＂ with terminal coordination azpy ligand acting as sidearms. Unprecedented three parallel interpenetrating two-dimensional (4,4) networks and novel infinite triple helices are formed via hydrogen-bonding interactions. CCDC: 155588.     

希夫碱钴配合物的吸氧热力学及其自氧化作用

本文合成了一个新的双Schiff碱钴配合物,并研究了该配合物在吡啶溶液中的吸氧过程热力学。在4—24℃范围内,吸氧摩尔比为1:1,吸氧过程热力学参数为:△H=-26.8(±0.5)kJ/mol,△S=-89.2(±1.8)J/mol·K。在30—45℃范围内,吸氧摩尔比为2:1,吸氧过程的热力学参数为:△H=-172.6(±9.14)kJ/mol,△S=-517.3(±29.4)J/mol·K。温度超过45℃,自氧化作用变得明显,配合物中苄羟基被氧化为醛基。提出了可能的氧化反应机理。