钐和钆对K10H3[Dy(SiW4Mo7O39)2]配合物的化学热扩渗及其导电性的研究

报道了Sm,Gd通过固 气界面反应对K10H3[Dy(SiW4Mo7O39)2]配合物的稀土多元渗。经ICP,IR测试表明:微量Sm,Gd可渗入到杂多配合物K10H3[Dy(SiW4Mo7O39)2]体相,XPS能谱分析证实了稀土元素的存在并与化合物有键合作用。采用四电极法对扩渗前后试样进行了导电性能的测定,扩渗后试样的导电率提高了0 9356×104倍。     

酰基吡唑啉酮缩氨基硫脲Ni(Ⅱ),Co(Ⅲ)和Cr(Ⅲ)配合物的合成、表征及生物活性

合成了含硫席夫碱1-苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5缩氨基硫脲(HL)及其Ni(Ⅱ),Co(Ⅲ)和Cr(Ⅲ)配合物.元素分析及摩尔电导率表明,新配合物的组成为[NiL2]·C2H5OH,[CoL2]Cl·H2O,[CrL2]Cl·1/2H2O.运用红外光谱、紫外光谱、核磁共振谱和磁矩对配合物进行了表征.抗菌实验表明,配合物具有较强的抗菌生物活性.     

[Si,N,N,P]体系异构体结构与稳定性

在B3LYP/6-311G(d)和QCISD(t)/6-311+G(2df)(单点)水平下计算得到了[Si,N,N,P]体系势能面上的一些驻点, 研究了异构体之间的异构化过程, 并讨论了该体系异构体的结构与稳定性. 结果表明在[Si,N,N,P]体系中的11个异构体中只有含有Si-P交叉成键的类蝶型四元环异构体SiNPN(E1, ²A″)是稳定的, 其他异构体由于易于重排或是解离, 稳定性较低. 研究同时给出了E1的电子与几何结构、振动频率及指认、偶极矩和转动常数等相关数据. 分析结果表明通过中间体E3(SiNPN)的反应SiN(²Π) + PN(¹Σ)→E1是由SiN(²Π)和PN(¹Σ)碎片产生E1的最有利途径, 因此E1可成为星际观测的目标. G2级别下此反应的反应焓变为215.25 kJ/mol (298.15 K), 而异构体E1在298.15 K下的标准生成焓为457.99 kJ/mol.     

锰为中心原子的三元杂多配合物的合成与氧化还原性质研究

用直接法合成了以锰为中心原子的过渡元素和钨的三元杂多配合物,经ICP和TG曲线确定其化学式为K5,6[MnM(OH2)W11O39]·xH2O(M=Mn2+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+和Cd2+),采用IR,UV,XRD和XPS等手段对配合物结构进行了表征,用循环伏安测定了其系列配合物的氧化还原性质,得出系列配合物的氧化性顺序,同时讨论配合物的热稳定性.     

一维链状2-氧-1(4H)-吡啶乙酸桥联钙配位聚合物[Ca(2-OPA)2(H2O)2]n的合成、晶体结构及热稳定性研究

A novel coordination polymer of [Ca(2-OPA)₂(H₂O)₂]_n (2-OPA-=2-oxo-1(4H)-pyridineacetate anion) was synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in orthorhombic with space group Pna2₁, a=0.799 96(16) nm, b=0.823 77(16) nm, c=2.415 3(5) nm, V=1.591 6(6) nm³, Z=4, R=0.030 3, wR=0.070 0. The Ca atom is eight-coordinated by six O atoms of four 2-OPA^- ligands and two water molecules, and displays a dodecahedron coordination geometry. Each 2-OPA^- ligand bridges two adjacent Ca atoms, forming a infinite chain along the a direction. The Ca…Ca distance is 0.4102 2(8)nm. A two-dimensional supramolecular framework is further constructed by the hydrogen bonds and the weak π-π interactions. The results of TG analysis show the chain structure of the title complex was stable under 297.5 ℃. CCDC: 251669.     

一维链状4-羧基苯氧乙酸桥联钴配位聚合物[Co(p-CPOA)(2，2′-bipy)(H2O)]n的合成与晶体结构

A novel coordination polymer of [Co(p-CPOA)(2，2′-bipy)(H₂O)]_n (p-CPOA^2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm³, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA^2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA^2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co…Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.     

OClO里德堡态激发能的准确预测及其阴离子低能激发态的从头算研究

采用全活化空间自洽场方法(CASSCF)研究了OClO阴离子7个低能电子态及其自由基的基态. 为了进一步考虑动态电子相关效应, 采用二级多组态微扰理论(CASPT2)获得更加可靠的能量值. 此外, 在ANO-L基组的基础上, 在OClO自由基的电荷中心增加了为研究里德堡态所建立的1s1p1d的波函数, 并应用多组态二级微扰理论(MS-CASPT2)方法获得了里德堡态的准确电子激发能.     

碱土金属钨铬杂多配合物的合成、表征及热稳定性研究

用直接法合成了以Cr为中心原子的碱土金属和W的三元杂多配合物,经ICP和TG曲线确定其化学式为K7[CrA(H2O)W11O39].xH2O(A=Mg2 ,Ca2 ,Sr2 和Ba2 ),采用IR,UV,XRD,XPS和183W NMR等手段对配合物结构进行了表征,确认所合成的配合物为-αKeggin结构.借助TG-DTA详细讨论了配合物的热稳定性,得出合成配合物的热稳定温度为450℃左右.     

介稳态氧化钨超微粉体的水热合成与光致变色性质研究

Under hydrothermal conditions, the superfine powders of cubic pyrochlore-type of tungsten oxide and hexagonal tungsten bronze were obtained by using Na₂WO₄·2H₂O as the starting material. The products were characterized by XRD, TG, IR, UV and EPMA, respectively. The effects of the pH value, the acid concentration, reaction temperature and time on the structure and particle size of products were investigated in detail. The conditions for the preparation of superfine powders of tungsten oxide were optimized. The pH 2.5～4.5 of the reaction system led to the formation of a pyrochlore phase and pH 0.5～2.0 gave the hexagonal tungsten bronze structure. The photochromism property of the hexagonal tungsten bronze was studied. The results show that pyrochlore and bronze phases are decomposed at 300 ℃ and 450 ℃, respectively. With the increasing of temperature, the structure of the two oxides changes. The pyrochlore-type powder changes completely into triclinic Na₂W₄O₁₃ around 500 ℃, while the bronze phase into a mixture of Na₂W₆O₁₉ and triclinic WO₃ at 550 ℃. The powder of the hexagonal tungsten bronze showed better photochromism property.     

一个结构新颖的含有反三棱柱结构单元的钴的多聚物的研究

采用1,4-二(1-H-苯并咪唑基)丁烷 (bbbi) 与CoSO₄•7H₂O反应得到一个结构新颖的金属—有机多聚物[Co(bbbi)_1.5(SO₄)]_n1. 在多聚物1中，中心离子Co(II)通过配体bbbi桥连在一起形成一个含有反三棱柱结构单元的二维层状结构. 每个反三棱柱结构单元由六个bbbi配体和六个Co(II)离子组成. 通过热分析我们发现，该化合物在147 ^oC以下是稳定的，若继续升温则被氧化并在787 ^oC时分解为 Co₂O₃，升温至914 ^oC时最终残余物为CoO。