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1.
二环己基-18-冠-6(DCH18C6)可以有效地从高放废液中分离90Sr,对于减小放射性废物的危害和实现高放废物的减容有重要意义.由于在实际应用中DCH18C6处于射线照射下,其结构可能会被破坏并引起络合能力的变化,因此有必要对该配合物的辐射稳定性进行研究.本文合成了Sr(NO3)2?DCH18C6配合物晶体,并通过单晶X射线衍射(XRD)与扩展X射线吸收精细结构谱(EXAFS)等方法进行了表征,确定Sr2+与周围氧原子的配位数为10,Sr―O平均键长约为0.268 nm/0.266 nm(XRD/EXAFS).配位原子来自DCH18C6的六个氧原子以及两个作为双齿配体的硝酸根的四个氧原子.对该配合物晶体在空气中进行γ辐照,EXAFS结果表明吸收剂量为400 kGy时,Sr―O键长及配位数没有发生变化,配位结构没有被破坏,具有很好的耐辐照稳定性.显微红外光谱(Micro-FTIR)结果进一步证明辐照后冠醚环的部分C―H键氧化为羟基或羰基,但并不影响DCH18C6与Sr2+的配位结构.  相似文献   

2.
应用从头算方法和ABEEM/MM浮动电荷分子力场, 研究了水合碱土离子团簇Sr2+/Ba2+(H2O)n (n=1-6), 构建了离子-水相互作用的ABEEM/MM势能函数, 获得了水合离子团簇的稳定结构, 计算了结合能. 计算结果表明, ABEEM/MM方法的结果和从头算方法的结果有很好的一致性. 进一步应用ABEEM/MM对Sr2+和Ba2+水溶液进行了分子动力学模拟. 对Sr2+水溶液, 得到的Sr2+-水中氧原子的径向分布函数的第一和第二最高峰分别位于0.257和0.464 nm处, 第一和第二水合层的配位水分子数分别为9.2和11.4; 对Ba2+水溶液, 得到的Ba2+与水中氧原子的径向分布函数的第一和第二最高峰分别位于0.269和0.467 nm处, 第一和第二水合层的配位水分子数分别为9.9和12.4. 这与实验值或其它理论模拟结果有较好的一致性. 对比外层的水分子, 金属离子的极化作用使得溶液中第一水合层中水分子的O―H键长增长, HOH键角减小.  相似文献   

3.
合成了配合物[Co(qina)2(H2O)2]•2DMSO单晶(qina为喹哪啶酸). 配合物属于单斜晶系, P2(1)/n空间群, 其分子结构为规则的八面体构型, qina以氮原子和羧酸根氧原子与Co2+离子配位, 两个水分子为轴向配位. 配合物之间富有配位水分子分别与DMSO的氧原子、qina中未与Co(II)配位的氧之间氢键作用. 配合物与鱼精DNA作用的紫外光谱和荧光光谱表明, 两者之间有一定的相互作用, 并可能以局部插入方式为主.  相似文献   

4.
高恩君  王克华  于影  尹洪喜  孙亚光 《化学学报》2007,65(16):1612-1616
合成了配合物[Co(qina)2(DMSO)2]单晶, 其中, qina为喹哪啶酸根, DMSO为二甲基亚砜. 配合物为单斜晶系, P2(1)/C空间群, 2个qina配体以氮原子和氧原子与Co(II)离子螯合配位, 2个DMSO以氧原子与Co(II)离子轴向配位, 形成规则的八面体构型配合物, 分子之间存在π-π堆积弱相互作用. 该配合物可显著提高乙酸-1-萘酯的水解速率, 在配合物浓度和萘酯浓度各为1.0×10-4和3.0×10-5 mol•L-1条件下, 酯的水解速率提高460倍.  相似文献   

5.
高恩君  程卯生  王克华  孙亚光 《化学学报》2006,64(21):2169-2172
合成了配合物[Co(qina)2(H2O)2]•2DMSO单晶(qina为喹哪啶酸). 配合物属于单斜晶系, P2(1)/n空间群, 其分子结构为规则的八面体构型, qina以氮原子和羧酸根氧原子与Co2+离子配位, 两个水分子为轴向配位. 配合物之间富有配位水分子分别与DMSO的氧原子、qina中未与Co(II)配位的氧之间氢键作用. 配合物与鱼精DNA作用的紫外光谱和荧光光谱表明, 两者之间有一定的相互作用, 并可能以局部插入方式为主.  相似文献   

6.
稀土配合物[Nd(o-NO2-C6H4COO)3(DMF)2]2的合成及其晶体结构   总被引:2,自引:0,他引:2  
赵丽芳  陈亚芍 《化学学报》2007,65(8):667-672
合成了一种新的双核倒反中心的稀土钕配合物[Nd(o-NO2-C6H4COO)3(DMF)2]2. 通过元素分析, 核磁共振谱和红外光谱对配合物的组成和结构进行了表征, 用热重分析研究了该配合物的热稳定性, 用X射线单晶衍射法测定了其晶体的结构. 钕配合物[Nd(o- NO2-C6H4COO)3(DMF)2]2晶体属三斜晶系, 空间群P-1, 晶胞参数a=1.18652(12) nm, b=1.24784(13) nm, c=1.29958(13) nm, α=64.220 (1)°, β=66.306 (1)°, γ=71.825 (1)°, V=1.5645 (3) nm3, Dc=2.167 mg/m3, Z=2, μ=3.415 mm-1, F(000)=986. 配合物中每个Nd(Ш)被4个邻硝基苯甲酸根桥联, Nd(Ш)的配位数为8, 配位原子分别来自于5个邻硝基苯甲酸羧酸根的6个氧原子和2个DMF的羰基氧原子. 配合物中的氢键和ππ 堆积作用使其成为三维立体结构. 同时发现了标题配合物固体具有光致发光现象, 发光性能测试表明该配合物具有很好的荧光性质.  相似文献   

7.
钌可以促使炔烃通过亚乙烯基钌卡宾金属配合物或钌金属杂环配合物的形式发生碳-碳偶联反应, 它的化学性质很大程度上取决于配体的电子和立体特征. 普通环戊二烯基钌配合物可以促使炔烃三聚生成苯环衍生物或使两分子炔烃和一分子含C=X键(X = C, O, S, N等)的不饱和底物发生环加成反应得到杂环化合物. 含桥联碳硼烷–环戊二烯基配体的钌乙腈配合物[η5:σ-Me2C(C5H4)(C2B10H10)]Ru(NCCH3)2 (1)表现出与环戊二烯基钌不同的反应性质. 例如, 配合物1与三甲基硅基取代的端炔或中间炔反应可生成含有单或双亚乙烯基有机钌卡宾配合物; 与末端芳炔则通过三分子炔和桥联配体中的环戊二烯基发生加成反应得到含有独特三环结构的有机钌配合物. 以上结果表明, 配体的位阻效应和炔烃的种类都可以影响产物的类型. 本文进一步研究了此钌乙腈配合物1与烷基或芳基取代的中间炔及中间二炔的反应. 配合物1与3-己炔或二苯乙炔在甲苯中于 80 ℃反应可以生成对空气和水稳定的η4-钌-环丁二烯配合物[η5: σ-Me2C(C5H4)(C2B10H10)]Ru(η4-C4Et4) (2) 或 [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(η4-C4Ph4) (3), 此反应相信是通过一个钌杂环戊三烯中间体进行的. 由于这个中间体既不能在反应中被分离到也不能在核磁反应中被监测到, 我们接下来尝试了1和1,6-二炔的反应. 在 1与2,7-壬二炔或3,8-十一碳二炔的反应中成功分离到钌杂环戊三烯配合物[η5: σ-Me2C(C5H4)(C2B10H10)]Ru[=C2- (Me)2C2(CH2)3] (4) 或 [η5: σ-Me2C(C5H4)(C2B10H10)]Ru[=C2(Et)2C2(CH2)3] (5). 化合物4与5 在甲苯回流温度仍然稳定. 由于位阻效应, 它们也不与苯乙炔、3-己炔、苯基异氰酸酯、二硫化碳以及叔丁基异腈反应. 以上新化合物通过了核磁和元素分析表征, 其中化合物2和4的结构得到了单晶X射线衍射确定. 在化合物2的晶体结构中, 钌原子通过η5-键与环戊二烯基配位, σ-键与硼笼相连, 以及η4-键与环丁二烯配位, 形成一个平面三角形结构. 在化合物4的晶体结构中, 钌原子通过η5-键与环戊二烯基配位, σ-键与硼笼相连, 以及与两个碳卡宾原子配位, 形成一个扭曲四面体构型. 钌与碳卡宾原子之间的键长显示其为Ru=C双键. 在以上实验结果基础上我们提出了1与炔烃反应生成2和3的反应机理: 钌-乙腈配合物通过与炔烃的配体交换反应得到钌-二炔配合物, 进一步氧化偶联得到钌杂环戊三烯中间体, 还原消除反应得到最终产物?钌-环丁二烯配合物. 在1与二炔的反应中, 4和5中的并环结构可以阻止还原消除反应, 从而起到稳定钌杂环戊三烯中间体的作用. 上述实验结果表明, 桥联碳硼烷配体和底物(炔烃)的空间位阻效应都对反应有很大的影响.  相似文献   

8.
合成了无水乳酸配合物(NH4)2[Sr(C3H5O3)4]。用X射线单晶衍射仪对该配合物的晶体结构进行了表征,确定了其组成、空间结构和配位方式。绘制了配合物的Hirshfeld表面和2D指纹图,揭示了分子间的相互作用以及该配合物具有多个配位位点和较强的配位活性。根据相关的晶体数据计算出了该配合物的晶格能及其对应阴离子的摩尔体积,计算得到该配合物的晶格能为2 742.9 kJ·mol-1。用等温环境反应-溶解量热计测量了该配合物在298 K超纯水溶剂中的溶解焓。根据Pitzer电解质溶液理论,在298 K下获得了该配合物的无限稀释摩尔溶解焓ΔsHm和Pitzer参数,确定该配合物的ΔsHm为(114.01±0.04) kJ·mol-1。计算了该配合物的表观相对摩尔焓(ΦL)以及不同浓度下溶质和溶剂的相对偏摩尔焓(L1L2)。最后,根据晶格能和ΔsHm设计了热化学循环,并计算出了阴离子的水合焓值。热重和微商热重曲线进一步揭示了该配合物的结构。  相似文献   

9.
沈娟  蒋琪英  钟国清  贾玉庆  郁开北 《化学学报》2007,65(16):1588-1592
合成了锑-镨与乙二胺四乙酸形成的新颖三维配合物[Sb24-(EDTA)2Pr(H2O)5]NO3•4H2O, 用元素分析、红外光谱、热分析及X射线单晶衍射法等进行了组成和结构表征. 结果表明该配合物属正交晶系, 空间群Pnn2; 晶胞参数: a=1.07031(2) nm, b=2.30805(4) nm, c=0.72343(2) nm, V=1.78711(7) nm3, Z=2, Dc=2.202 g/cm3, F(000)=1164, μ=2.955 mm-1, GOF=1.000, 最终偏离因子R1=0.0203, wR2=0.0545 [I>2σ(I)]. 在标题化合物中, 每个镨(III)离子的配位数为9, 与五个水分子中的五个氧原子和四个羧基氧原子配位, 形成三帽三角棱柱空间配位多面体. 锑(III)与EDTA离子中的四个氧原子和两个氮原子配位, 在赤道平面上有一孤对电子. 同时讨论了配合物的热分解过程.  相似文献   

10.
合成了一个配位聚合物{[Cd(pdc)(bbi)]·2H2O}n(H2pdc=2,3-吡啶二甲酸,bbi=1,4-二咪唑基丁烷),利用元素分析、红外光谱和X-射线单晶衍射考察了配合物的结构。配合物中,Cd(Ⅱ)的配位数为5,每个Cd(Ⅱ)与1个吡啶二甲酸离子的1个羧基氧原子和吡啶氮原子,另1个吡啶二甲酸离子的1个羧基氧原子,以及2个1,4-二咪唑基丁烷的2个氮原子配位。吡啶二甲酸离子的配位方式可以表示为μ-(κ3N,O2:O3),Cd(Ⅱ)与之连接形成一维骨架链[Cd(pdc)]。配体1,4-二咪唑基丁烷采用了“Ω”和“S”两种构型,它们进一步与中心原子配位形成三维网络结构。配合物为三重穿插的金刚石型网络结构,拓扑学符号为66。受光激发,该配合物在426nm处有一个发射峰。  相似文献   

11.
The complexation reactions between Mg2+,Ca2+,Sr2+ and Ba2+ metal cations with macrocyclic ligand, dicyclohexano-18-crown-6 (DCH18C6) were studied in methanol (MeOH)–water (H2O) binary mixtures at different temperatures using conductometric method . In all cases, DCH18C6 forms 1:1 complexes with these metal cations. The values of stability constants of complexes which were obtained from conductometric data show that the stability of complexes is affected by the nature and composition of the mixed solvents. While the variation of stability constants of DCH18C6-Sr 2+ and DCH18C6-Ba2+versus the composition of MeOH–H2O mixed solvents is monotonic, an anomalous behavior was observed for variations of stability constants of DCH18C6-Mg2+ and DCH18C6-Ca2+ versus the composition of the mixed solvents. The values of thermodynamic parameters (ΔHc°, ΔSc°) for complexation reactions were obtained from temperature dependence of formation constants of complexes using the van’t Hoff plots. The results show that in most cases, the complexation reactions are enthalpy stabilized but entropy destabilized and the values of thermodynamic parameters are influenced by the nature and composition of the mixed solvents. The obtained results show that the order of selectivity of DCH18C6 ligand for metal cations in different concentrations of methanol in MeOH–H2O binary system is: Ba2+>Sr2+>Ca2+> Mg2+.  相似文献   

12.
采用密度泛函理论广义梯度近似平面波赝势法,结合周期平板模型,探讨了水体环境中Pb(OH)+在高岭石铝氧八面体(001)晶面的吸附行为和机理,确定了吸附配合物的结构、配位数、优势吸附位和吸附类型.结果表明,Pb(II)与高岭石铝氧(001)面的氧原子形成单齿或双齿配合物,其配位数为3-5,均为半方位构型.高岭石表面存在含"平伏"氢原子的表面氧(Ol)位和含"直立"氢原子的氧(Ou)位,后者更易与Pb(OH)+单齿配位,该吸附配合物具有较高的结合能(-182.60 kJ·mol-1),为优势吸附物种;高岭石表面位于同一个Al原子上的"OuOl"位可形成双齿配合物.表面Ol与水分子配体形成氢键,对配合物的稳定性起到关键作用.Mulliken布居和态密度分析表明,高岭石单齿配合物中Pb―O成键机理主要为Pb 6p轨道与Pb 6s―O 2p反键轨道进行耦合,电子转移到反键轨道.双齿配合物"Pb―Ol―H"共配位结构中,受配位氢原子影响,Pb―Ol成键过程成键态电子填充占主导地位.  相似文献   

13.
In this work, Sr3Al2O6: Eu2+ (Eu3+), Dy3+ phosphors have been prepared by hydrothermal treatment and subsequently postannealing approach, using Sr(NO3)2, Al(NO3)3·9H2O, and CO(NH2)2 as starting materials. The as-obtained phosphors were characterized by means of XRPD, FESEM, and PL techniques. In addition, many reaction parameters were studied in detail, including the initial mole ratios, hydrothermal reaction temperature, calcination temperature and calcination atmosphere. Remarkably, two scientific merits exist herein: Sr3Al2O6: Eu2+ (Eu3+), Dy3+ phosphors can be selectively obtained in a reducing atmosphere (H2/Ar, 20%+80%) and in air, respectively; adding certain amount of sodium citrate can alter the shape and size of Sr3Al2O6: Eu2+ (Eu3+), Dy3+ phosphors in essence. Besides, the luminescent properties of Sr3Al2O6: Eu2+ (Eu3+), Dy3+ phosphors were studied by excitation spectra, emission spectra and decay curves.  相似文献   

14.
The complexation reactions between Mg2+, Ca2+, Sr2+ and Ba2+ cations with the macrocyclic ligand, 18-Crown-6 (l8C6) in water–methanol (MeOH) binary systems as well as the complexation reactions between Ca2+ and Sr2+ cations with 18C6 in water–ethanol (EtOH) binary mixtures have been studied at different temperatures using conductometric method. The conductance data show that the stoichiometry of all the complexes is 1:1. It was found that the stability of 18C6 complexes with Mg2+, Ca2+, Sr2+ and Ba2+ cations is sensitive to solvent composition and in all cases, a non-linear behaviour was observed for the variation of log K f of the complexes versus the composition of the mixed solvents. In some cases, the stability order is changed with changing the composition of the mixed solvents. The selectivity order of 18C6 for the metal cations in pure methanol is: Ba2+ > Sr2+ > Ca2+ > Mg2+. The values of thermodynamic parameters (Δ H c ° and Δ S c °) for formation of 18C6–Mg2+, 18C6–Ca2+, 18C6–Sr2+ and 18C6–Ba2+complexes were obtained from temperature dependence of the stability constants. The obtained results show that the values of (Δ H c ° and Δ S c °) for formation of these complexes are quite sensitive to the nature and composition of the mixed solvent, but they do not vary monotonically with the solvent composition.This revised version was published online in July 2005 with a corrected issue number.  相似文献   

15.
The crystal structure of strontium dialuminodiborate SrAl2B2O7 has been established by single-crystal X-ray diffraction methods. The compound crystallizes in the trigonal system (space group R c, Z=6) with cell parameters a=4.893(1) Å and c=47.78(1) Å. Aluminium and boron atoms are, respectively, in tetrahedral and triangular oxygen coordination. The assembly of Al2O7 units and BO3 triangles forms double layers between which Sr2+ ions are located. The Eu2+-doped crystalline powder exhibits a luminescence band with maximum at 415 nm. Luminescence characteristics are compared to those of other strontium borates.  相似文献   

16.
由摩尔比分别为1:2和1:8的NiCl2·6H2O和Na2B4O7·10H2O作为反应物, 合成两种非晶态镍硼酸盐, 同时通过水热法合成β-Ni(OH)2. 化学分析和热重-微商热重法(TG-DTG)分析结果确定两种非晶态镍硼酸盐的分子组成分别为NiO·0.8B2O3·4.5H2O和NiO·B2O3·3H2O. 激光拉曼(Raman)实验结果表明镍硼酸盐样品中主要存在的硼氧阴离子为B3O3(OH)52-和B2O(OH)62-. 同步辐射扩展X射线吸收精细结构(EXAFS)方法对样品进行结构解析, 通过数据拟合给出样品中Ni 原子周围近邻配位原子种类、配位数以及原子间距离. 用不同晶体结构作为标准对两种非晶态镍硼酸盐进行拟合的结果表明, 样品中Ni 原子周围局域结构与Ni3B2O6晶体(ICSD No.31387)中的吻合较好. Ni 原子周围配位原子为O、B和Ni, 对于NiO·0.8B2O3·4.5H2O, 配位数分别为5.7、3.8和3.8, 配位距离分别为0.208、0.263 和0.311 nm; 对于NiO·B2O3·3H2O, 配位数分别为6.0、4.0 和4.0, 配位距离分别为0.207、0.262和0.310 nm.  相似文献   

17.
A new red-emitting long afterglow Sr3Al2O6: Eu2+, Pr3+ phosphor was synthesized by sol–gel methods using Sr(NO3)2, Al(NO3)3·9H2O, Eu(NO3)3 and Pr(NO3)3 as raw materials. The crystalline structure of the phosphor powders were characterized by X-ray diffraction. Luminescent properties of the phosphor powders were analyzed by the fluorescence spectrophotometer. Sr3Al2O6: Eu2+, Pr3+ phosphor powders with single Sr3Al2O6 phase were prepared at 1200 °C for 2 h in the reducing atmosphere. Pr3+ doped made the light intensity and the light-lasting time of Sr3Al2O6: Eu2+, Pr3+ phosphors improved. The emission peaks of the Sr3Al2O6: Eu2+, Pr3+ phosphor powders lay at 612 nm with the excitation of 472 nm and the longest afterglow time could last for about 15 min at Pr3+ content of 0.06.  相似文献   

18.
The complex formation between La3+, UO22+ Ag+, and NH4+ cations and macrocyclic ligand, dicyclohexyl-18-crown-6 (DCH18C6), was studied in acetonitrile-tetrahydrofuran (AN-THF) binary mixtures at different temperatures using the conductometric method. The results show that with the exception of complexation of the NH4+ cation with DCH18C6 in pure acetonitrile, the stoichiometry of all the complexes is being 1: 1 (M: L). The stability constants of the complexes were determined using a GENPLOT computer program. The nonlinear behavior which was observed for changes of log K f of the complexes versus the composition of the mixed solvent was discussed in terms of solvent-solvent interaction in their binary solution, which results in changing the chemical and physical properties of the constituent solvents when they mix with one another and, therefore, changing the solvation capacities of the metal cations, crown ether molecules, and even the resulting complexes with changing the mixed solvent composition. The results show that the selectivity of DCH18C6 for the studied cations changes with the composition of the AN-THF binary system. The sequence of stabilities of complexes in an AN-THF binary solution (mol. % AN = 75.0) at 25°C is [(DCH18C6)La)]3+ > [(DCH18C6)UO2]2+ > [(DCH18C6)Ag]+ ∼ [(DCH18C6)NH4]+, but in the case of other binary systems of AN/THF (mol. % AN = 25.0 and 50.0) is [(DCH18C6)La]+ > [(DCH18C6)NH4]+ ∼ [DCH18C6)UO2]2+ > [(DCH18C6)Ag]+. The text was submitted by the authors in English.  相似文献   

19.
A novel red light-emitting material, Ca3Al2O6:Eu3+, which is the first example found in the Ca3Al2O6 host, was prepared by calcination of a layered double hydroxide precursor at 1350 °C. The precursor, [Ca2.9−xAl2Eux(OH)9.8](NO3)2+x·2.5H2O, was prepared by coprecipitation of metal nitrates with sodium hydroxide. The material is a loose powder composed of irregular particles formed from aggregation of particles of a few nanometers, as shown in scanning electron microscope (SEM) images. It was found that the photoluminescence intensity reached the maximum when the calcination temperature was 1350 °C and the concentration of Eu3+ was 1.0%. The material emits bright red emission at 614 nm under a radiation of λ=250 nm.  相似文献   

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