3,6-二-[二甲胺基]-二苯并六碘圜氯化物的晶体结构与分子结构

标题化合物的分子式为C₁₇H₂₀N₂ICl,熔点197.5℃(分解)。经甲醇-氯仿(1:1)重结晶,得淡黄色六棱柱状单晶。 晶胞参数经CAD-4四圆衍射仪测定精修,结果为:a=11.073(2),b=13.766(1),c=11.229(11)Å,β=99.36(5)°,Z=4,ρ_cal=1.631g/cm³(ρ_obs=1.60g/cm³)。 衍射强度数据在CAD-4四圆衍射仪上收集,所用单晶大小约0.3×0.3×1.2mm³。     

一个钼钒二聚体簇合物的合成及其性能

以NH₄VO₃, H₃PMo₁₂O₄₀·xH₂O, Cu(NO₃)₂和哌嗪为主要原料,采用水热方法,合成了一个新的钼钒二聚体簇合物--(H₂NC₄H₈NH₂)₆［Mo^VI₁₆V^V₁₂P₂O₈₄］·5H₂O(1),其结构和性能经UV-Vis, IR, X-射线衍射、光电子能谱及热重分析表征。1属单斜晶系,P2(1)/c空间群, 晶胞参数a=20.450(4) , b=24.989(5) , c=20.450(4) , β=93.89 °, V=10 427(4) ³, Fw=4 159.18, Dc=2.650 g·cm^-3, μ=3.018 mm^-1, F(000)=7 952, Gof=1.029。晶体结构解析表明：1由两个单元Keggin型簇核［PMo₈V₆O₄₂］^7-聚合而成一个二聚体簇［P₂Mo_l6V₁₂O₈₄］^14-,该二聚体簇核和有机配体哌嗪之间通过复杂的氢键相互作用,展示三维超分子网络结构。     

278.15～318.15 K下葡萄糖在盐酸中的体积性质

测定了278.15～318.15 K(间隔10 K)下葡萄糖＋HCl＋水三元体系的密度, 计算了葡萄糖在盐酸(浓度0.2～2.1 mol•kg^–1)中的表观摩尔体积V_Φ,G、标准偏摩尔体积V⁰_Φ,G、葡萄糖-HCl在水中的体积对相互作用参数V_EG和标准偏摩尔膨胀系数(∂V⁰_Φ,G/∂T)_p. 结果表明: (1)葡萄糖在盐酸中的表观摩尔体积随葡萄糖和HCl的浓度的增加而线性增大; (2) V⁰_Φ,G随HCl的质量摩尔浓度的增加而线性增大; (3)葡萄糖与HCl在水溶液中的体积相互作用参数V_EG＞0, 但数值对温度变化不甚敏感; (4)葡萄糖在水和盐酸中的V⁰_Φ,G值随实验温度的变化关系均可表示为: V⁰_Φ,G＝a₀＋a₁(T－273.15 K) ^2/3; (5) (∂V⁰_Φ,G/∂T)_p为正值且随温度的升高而减小; 在一定温度下, 其值随HCl浓度的增加而稍稍减小. 糖的水化程度随温度的升高和HCl的浓度的增加而减小. 用结构相互作用模型对葡萄糖与HCl之间的体积相互作用进行了解释.     

分散共聚合制备PSt-AA-EGDMA功能性单分散微米级交联微球的研究

以苯乙烯(St)为主单体,丙烯酸(AA)为功能单体,乙二醇二甲基双丙烯酸酯(EGDMA)为交联单体,聚乙烯吡咯烷酮(PVP)为稳定剂,偶氮二异丁腈(AIBN)为引发剂,乙醇/水混合溶剂为分散介质,用分散聚合法一步合成了功能性单分散大粒径(10～20μm)交联聚苯乙烯微球.研究了PSt-AA-EGDMA三元分散共聚合体系的动力学,由转化率-时间关联得到动力学方程;R_p=k[I]^0.13([St]^1.87+[AA]^0.13+[EGDMA]^0.2)·(1+[PVP]^0.2)exp(-E/RT).详细讨论了AA,EGDMA,PVP的浓度和溶剂极性对羧基分布的影响,阐述了AA和EGDMA对粒子形态、粒径及粒径分布的影响.     

4-(4-羧基苯氧基)间苯二甲酸构筑的过渡金属配位聚合物: 合成、 晶体结构、 荧光传感与光催化

采用水热法合成了4个配位聚合物[Zn(Hcpoia)(2,2'-bpy)·H₂O]_n(1)和[M(Hcpoia)(phen)]_n·nH₂O[M=Zn(2), Mn(3), Co(4); H₃cpoia=4-(4-羧基苯氧基)间苯二甲酸; 2,2'-bpy=2,2'-联吡啶; phen=1,10-邻菲罗啉], 利用X射线单晶衍射分析确定了配合物的晶体结构. 配合物1为一维链状结构, 中心Zn ²⁺离子的配位环境为[ZnO₄N₂]扭曲的八面体构型, 配体Hcpoia ^2-以μ₁∶η ¹η ⁰和μ₁∶η ¹η ¹配位模式桥连相邻的Zn ²⁺离子. 配合物2和4的结构与配合物1类似, 是由配体Hcpoia ^2-以μ₁∶η ¹η ⁰和μ₁∶η ¹η ¹配位模式联接[MO₄N₂]结构单元而形成的一维链状结构. 配合物1, 2和4中均存在分子间氢键(O—H…O), 氢键的存在使一维链连接形成二维超分子结构. 配合物3为二维网状结构, Mn ²⁺离子的配位环境为[MnO₄N₂]扭曲的八面体构型, 配体Hcpoia ^2-以μ₂∶η ¹η ¹配位模式桥连相邻Mn ²⁺离子形成[Mn₂COO₂]结构单元, 该结构单元被Hcpoia ^2-连接形成二维结构. 在4个配合物中, 2,2'-bpy和phen配体均以端基的形式与金属离子螯合配位. 研究了水溶液中抗生素分子和Fe ³⁺离子对配合物1与荧光强度的影响, 实验结果表明, 甲硝唑、 Fe ³⁺离子对配合物1有荧光猝灭作用, 并进一步考察了甲硝唑浓度和Fe ³⁺离子浓度对配合物1荧光强度的影响. 基于荧光猝灭机理, 配合物1可以用作荧光传感器检测水溶液中的甲硝唑和Fe ³⁺离子. 研究了配合物4对罗丹明B(RhB)的催化降解性能, 发现在氙灯照射和H₂O₂存在条件下, 配合物4对RhB具有较好的光催化降解作用.     

电位法测定烟酸银络合物的稳定常数

在25℃、有2MKNO_s存在的条件下,用电位法测定银与烟酸络合物的稳定常数.测定结果:β₁=2.50×10²,β₂=1.38×10⁴.     

三(三甲基硅)环戊二烯与六羰基钼的反应

三(三甲基硅)环戊二烯与六羰基钼在二甲苯中回流8h,反应停留在生成中间物η⁵-[(Me₃Si)_NC₅H_5-n]Mo(CO)₃H(n=2,3)(I)的阶段.不经分离,I随即分别与CCl₄·NBS及MeI反应,生成其相应的钼卤化物η-⁵[(Me₃Si)_NC₅H_5-n]Mo(CO)₃X[n=3,X=Cl(1),Br(2),I(3);n=2,X=Cl(4),Br(5),I(6)].4-6是由于茂环上脱掉1个Me₃Si基.经元素分析和IR及¹H NMR谱表征了化合物1-6的结构,并用X射线衍射测定了1的晶体结构.     

基于萘酰亚胺-苯并咪唑鎓的荧光传感器对H2PO-4的高选择性识别

设计合成了基于萘酰亚胺-咪唑鎓的受体分子1和2,通过荧光发射光谱研究了受体分子1和2对阴离子F^-、Cl^-、Br^-、I^-、AcO^-、HSO^-₄、H₂PO^-₄、NO^-₃、ClO^-₄的识别性能。 研究发现,在受体分子1和2的乙腈溶液(5.0×10^-6 mol/L)中加入10倍化学计量的H₂PO^-₄时,受体分子1的荧光猝灭率高达98%,受体分子2的荧光猝灭率仅为24%。 表明具有多重识别位点的受体分子1在构型上与H₂PO^-₄更匹配,可作为H₂PO^-₄的荧光关闭型(turn-off)探针。 受体分子1与H₂PO^-₄的结合比为1∶1,结合常数为(1.25±0.11)×10⁵ L/mol,检出限为6.90×10^-6 mol/L。     

昆虫性信息素顺-9-十四碳烯-1-醇乙酸酯的合成

顺-9-十四碳烯-1-醇乙酸酯(1)是鳞翅目许多昆虫的性信息素或其组分之一^[1]。已报道的化合物1的合成方法是采取C₁₀+C₄或C₉+C₅偶联原则^[2]。本文报道另一条合成路线(图1),采取C₈+C₆原则,以1,8-辛二醇(2)为原料,经过ω-氯代辛醇(3)得2-(8'-氯辛烷-1-氧基)四氢吡喃(4)^[2d],卤代物4与己炔-1(5)^[3]的锂盐缩合得炔化物6,然后以Lindlar催化剂^[4]进行部分氢化,粗产品7无需分离可直接去保护基并乙酞化得产物1,五步的总得率约40%.     

芳基亚胺-脒基稀土烷基化合物的合成及其催化异戊二烯聚合研究

制备了芳基亚胺-脒基稀土二烷基化合物[NNN]Ln(CH₂SiMe₃)₂ {[NNN]=[2-C(H)NDippC₆H₃NHC(Ph)NDipp], Dipp=2,6-i-Pr₂C₆H₃, Ln=Y (2), Sm (3)}, 2和3通过了¹H NMR, ¹³C NMR, IR和元素分析测试, 通过X-ray确定了化合物2的晶体结构. 加入[Ph₃C][B(C₆F₅)₄]和烷基铝, 两个化合物均能高效催化异戊二烯聚合, 具有较好的3,4-选择性(88%), 中等的立体选择性(rr=50%), 较高的分子量(M_n=6.8×10⁴)和较窄的分子量分布(M_w/M_n=1.15). 同时发现, 烷基铝和[Ph₃C][B(C₆F₅)₄]的比例影响催化聚合的区域选择性.     

Spectroscopic investigation of ground state pyrrole (C4H5N): the NH stretch

We have recorded the infrared absorption spectrum of pyrrole at 0.005 cm⁻¹ spectral resolution using a Fourier transform interferometer. The rotational analysis of the fundamental N---H stretch (1¹₀) at 3530.811343(82) cm⁻¹ was performed. A set of 13 upper state rovibrational parameters was determined, allowing the 2715 assigned rovibrational lines to be reproduced with a standard deviation of 1.3 10⁻³ cm⁻¹. An attempt to record the fundamental band under slit-jet conditions is reported. The role of hot bands accompanying the series of the N---H stretch excitation is investigated. Effective vibrational parameters — ω⁰₁, X⁰₁₁, Y₁₁₁, X_1,24 — are obtained. The lower level in the hot band series is unambiguously identified as the V₂₄ = 1 level, by retrieving X_1,24 independently, from other spectral data. The observation of the complex band pattern accompanying the N---H series in the higher overtone range is discussed with the help of new data, recorded around the 1⁵₀ band at different temperatures using intracavity laser optoacoustic spectroscopy.     

Hydrothermal Syntheses and Characterization of Two 1D Chain Complexes and Tetra-capped Keggin Clusters

Two new compounds, [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₆Mo^V₂V^IV₈O₄₀(SiO₄)]}[(NH₂)₂(C₂H₄)₂NH]·2H₂O(1) and [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(VO₄)]}(en)·H₂O(2)(en=ethylenediamine), have been hydrothermally synthesized and characterized by elemental analysis, infrared(IR), X-ray photoelectron spectroscopy(XPS), electron spin-resonance(ESR) and thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD) analysis. Both the compounds exhibit a 1D chain composed of bi-supporting tetra-capped Keggin clusters and nickle coordination fragments. The 1D chains are further assembled into a 3D supramolecular network with different packing modes via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrates the presence of antiferromagnetic interactions.     

Laser-induced population depletion effects in double resonance excitation with Hg vapors

By monitoring the green fluorescence transition of mercury vapor 7 ³S₁→6 ³P⁰₂ (546.074 nm) excited by two pulsed dye lasers tuned at two connected atomic resonant frequencies, i.e. 6 ¹S₀→6 ³P⁰₁ (253.652 nm) and 6 ³P⁰₁→ 7 ³S₁ (435.835 nm), a decrease in the green fluorescence yield is experimentally observed when the intensity of the 435.835-nm excitation transition exceeds 5 kW/cm². A similar result is obtained at the yellow fluorescence transition 6 ³D₁→6 ¹P⁰₁ (578.967 nm) when the second step is tuned to the 6 ³P⁰₁→6 ³D₁ transition (313.159 nm). At the same time, an increase in the transmittance of the ground state transition (253.652 nm) is observed. It is speculated that this effect, which occurs only when both laser pulses are temporally coincident, and is therefore not due to photoionization, can be ascribed to the existence of laser induced effects, such as a.c. Stark splitting of levels and possibly electromagnetically-induced transparency (EIT). Our experiment does not allow us to distinguish between these two effects, nor their quantitative evaluation. However, it is stressed that one cannot overlook them in those atomic multi-step excitation experiments in low collisional environments where a depletion of an intermediate level is involved, as for example in the case of atomic fluorescence dip spectroscopy or atomic multistep and multiphoton resonance ionization spectroscopy.     

Coordination-driven self-assembly of palladium(Ⅱ)-based metallacalixarenes as anion receptors using flexible pyridine-bridged diimidazole ligands

Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]²⁺and[ML₂]²⁺have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L¹),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L²),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L³)],with palladium(II)-based building blocks[Pd(BF₄)₂(M¹-BF_4)and(tmeda)Pd(NO₃)₂(M²-NO₃)(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(¹H NMR and¹³C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M¹L²_2](NO₃)₂,[M¹L³_2](NO₃)₂,[M¹L³_2](PF_6)_2 and[M~2 L³](NO₃)₂further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO.     

A Au mössbauer study of reaction products of trimeric 1-benzyl-2-gold(I)-imidazole leading to Au carbene or Au imidazoline complexes and trinuclear Au imidazolyl derivatives. X-Ray crystal structure of [{(μ-1-benzylimidazolato-N,C)Au}3I2]

Reactions of the trinuclear [Au₃Rim₃] compound (Rim = [μ-1-benzylimidazolato-N³,C²] with several reagents capable of oxidative addition have been investigated by ¹⁹⁷Au Mössbauer spectroscopy. The reaction products are either Au^I carbene mononuclear and binuclear complexes or trinuclear Au^III and mixed-valence compounds. The X-ray crystal structure of the mixed-valence complex [Au^IIIAu^I₂Rim₃I₂] has been determined. Two two-coordinate Au^I centres show average Au---C and Au---N distances of 2.02(3) and 2.04(2) Å and average C---Au---N angles of 175.0(1.2)°, whereas the four-coordinate Au^III centre gives Au---C and Au---N 1.96(4) and 1.91(3) Å with the C---Au---N angle 170.5(1.6)°, and Au---I average distances 2.598(3) Å, with an I---Au=I angle 175.8(1)°. The Au---Au intramolecular distances [Au(1) Au(2) 3.432(3), Au(1) Au(3) 3.508(3), Au(2) Au(3) 3.464(3) Å] indicate a weak metal-metal interaction.     

新型一维麻花状超分子配合物的合成与结构

具有特殊结构及性能的超分子化合物由于其结构上的新颖性及潜在的应用价值而成为人们关注的热点 .以一个苯环为间隔基两端含两个吡啶基团的配体 L1与 Pd( ) ,Pt( )形成 2 -索烃 [1 ] ,与Cd( NO3) 2 则形成具有一维平面结构的聚合物 [2 ] .以联苯为间隔基的配体 L2在 4 ,4′-二联吡啶共同作用下与 Pd( )形成 2 -索烃 [3] .同样以一个苯环为间隔基两端含两个咪唑基团的配体 L3与 Zn( NO3) 2 ,Ag NO3反应得到新型多聚轮烷配合物 [4,5 ] .研究结果表明 ,配体或配位金属离子等的微小差别即导致形成结构不同的超分子化合物 .但这些超分子…     

新的四帽Keggin结构的金属-氧簇合物[NiMo12O40H10{Ni(H2O)3}4]的水热合成与结构表征

多金属氧酸盐 (也称金属 -氧簇 )由于在催化、材料及医药等领域的应用日益广泛而备受关注 .近年来 ,一些新颖的非经典结构的化合物不断被合成出来 .如带二帽的 Keggin结构化合物 [V15O4 2 ]9- [1] ,[PV14 O4 2 ]9- [2 ] ,[As V14 O4 2 ]9- [3 ] ,[{ Mo8V7O4 2 } 2 ]14 - [4 ] ,     

Two-centre model potential energy calculations for the Σ and Π states of Li2, Na2, K2, Rb2 and Cs2

Two-centre model potential calculations have been carried out for the ²Σ⁺_g,u and ²Π_g,u states of Li⁺₂, Na⁺₂, K⁺₂, Rb⁺₂ and Cs⁺₂. Comparison with other model potential calculations suggests that reliable potential curves have been obtained. The results indicate the usefulness of calculating diatomic energies by the method proposed.     

Synthetic [FeFe]-H2ase models bearing phosphino thioether chelating ligands

Through the oxidation-reduction combination procedure, the neutral tri-substituted {2Fe3S} complex 2 was synthesized by replacing the CO ligand in 1 with phosphine. This substitution leads to the Fe-Fe bonds in 1 and 2 with large Lewis basicity difference, i.e. △pK_a^MeCN~10.