Dimerization and Coordination Properties of Zinc(II)tetra-4-alkoxybenzoyloxiphthalocyanine in Relation to DABCO in <Emphasis Type="Italic">o</Emphasis>-Xylene and Chloroform

For the first time the interactions between zinc(II)tetra-4-alkoxybenzoyloxiphthalocyanine (Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc) and 1,4-diazabicyclo[2.2.2]octane (DABCO) in o-xylene and chloroform have been studied by calorimetric titration and NMR and electron absorption spectroscopic methods. It has been found that in o-xylene at concentrations of Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc higher than 6×10⁻⁴ mol⋅L⁻¹ π–π dimers species are formed (λ _max= 685 nm). Additions of DABCO to the solution up to mole ratio 1 : 8 (Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc : DABCO) lead to a shift of the aggregation equilibrium towards monomer species due to formation of monoligand axial complexes. Further increasing the DABCO concentration results in formation of Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc—DABCO—Zn(4—O—CO—C₆H₄—OC₁₁H₂₃)Pc sandwich dimers (λ _max= 675 nm).     

3-苯基-1-丁炔-3-醇质谱碎裂中[C8H7]^+的结构及分子内质子迁移反应

报道了3-苯基-1-丁炔-3-醇的常规电子轰击质谱(EIMS)。利用碰撞诱导解离(CID)技术研究了质谱碎裂过程中产生的[C8H7]^+的气相离子结构。同时, 氘代同位素交换、亚稳(MI)和CID实验进一步证实了m/z 103离子的形成并不是分子离子的质谱碎裂中顺次失去甲基自由基和中性CO分子的直接氢迁移的协同反应, 而是在失去CO分子前后发生了二次质子迁移反应的逐步过程。在此基础上提出了一种独特的双分子质子键合复合物中间体的碎裂机理。     

Two-electron atomic wave functions which satisfy proportionality relations between one-and two-electron moments

Based on momentum- and position-space analyses of the moment operators for two-electron atoms, it is shown that there exists a family of two-electron wave functions which satisfy a proportionality relation, r/ ₁ ^v /r ₁₂ ^v =p/ ₁ ^v /p ₁₂ ^v =2^–v/2, between the one and two-electron moments in position and momentum spaces, where v is an arbitrary number for which the moments are well-defined.     

Synthesis and Crystal Structure of cis-Bis(3-hydroxy2-ethyl-4-pyranonato)dioxomolybdenum(Ⅵ)

1 INTRODUCTION 3-Hydroxy-2-methyl-4-pyranone (maltol) and 3-hydroxy-2-ethyl-4-pyranone (ethylmaltol) are nontoxic compounds that have been applied to bio- inorganic chemistry over several decades[1, 2]. Their iron(III) complexes are relevant to the control of iron levels in the human body. Such complexes have been assessed for the amelioration of anaemia[3] and their respective ligands have been tested for the removal of excess burdens of iron in diseases such as siderosis, haemochroma…     

A new polyphenol modified electrode containing an anchored ruthenium complex and its use in electrocatalytic oxidation of organic substrates

This work describes the preparation of a new modified electrode containing a ruthenium complex (cis-aquadimethylbipyridyltriphenylphosphineruthenium II), bonded to a stable polyphenol film. This modified electrode promotes the fast electrocatalytic oxidation of safrol (5-allyl-benzo[1,3]dioxole) and isosafrol (5-propenyl-benzo[1,3]dioxole), giving two interesting products benzo[1,3]dioxole-5-carbaldehyde (piperonal) and 3-benzo[1,3]dioxol-5-yl-propenal respectively, with good yields. The electrode preparation can be carried out at a potential range which does not interfere on the anchored electroactive ruthenium complex, but it allows for the phenol oxidation to occur and therefore polymerize forming the polyphenol film. The catalytic character of this modified electrode is showed by its high turnover numbers. The procedure to isolate the products is very simple.     

双核锌配位化合物[Zn(C15H8O7S)(DMSO)]2•H2O的合成和晶体结构及光致发光性能研究

以白杨素为先导化合物, 对其进行磺化, 磺化衍生物与锌络合, 在含水10%的二甲基亚砜(DMSO)溶液中重结晶, 得双核锌配位化合物[Zn(C₁₅H₈O₇S)(DMSO)]₂•H₂O. 采用IR, ¹H NMR, DSC-TGA, 元素分析和X射线单晶衍射法对标题化合物进行了表征和晶体结构测定. 标题化合物属正交晶系, 空间群Pbcn, Zn(II)的配位数为5, 配位原子均为氧原子, 每个五配位的锌都具有四方锥型的配位构型, 被2个配体5-羟基氧负离子-7-羟基黄酮-6-磺酸根的5-羟基氧负离子桥联, 形成了一个中心Zn₂O₂的菱形平面. 水溶性白杨素黄酮配体与Zn(II)通过氢键、π-π堆积和配位作用自组装形成了一个三维结构的超分子化合物. 差示扫描量热分析(DSC-TGA)结果表明,标题化合物配体骨架分解温度为518.26 ℃. 同时, 标题化合物固体具有较强的光致发光现象, 在λ_ex＝423 nm条件下可发出λ_em＝488 nm的黄色荧光, 并对其发光机制进行了探讨.     

苯乙烯-马来酸酐自由基共聚反应 (Ⅰ)苯乙烯-马来酸酐电荷转移络合反应

电荷转移络合反应机理是研究苯乙烯－马来酸酐自由基交替共聚反应机理的关键。本文简述了苯乙烯－马来酸酐电荷转移络合反应的研究进展。     

Application of chiral thiazolidine ligands to asymmetric hydrosilation

Seven chiral thiazolidines bound rhodium complexes were synthesized and their catalytic asymmetric hydrosilation properties were investigated It was found through investigation that the configuration of newly formed chiral centre C2 of substituted chiral thiazolidines prepared from L-cysteine or its esters has no effect on the final results of catalytic asymmetric hydrosilation.The direct reason for causing this phenomenon is reported by the present quantitative results for the first time:the rapid racemation of chiral center C2 of chiral thiazolidine ligands takes place under the catalysis of rhodium(Ⅰ) complex [Rh(COD)CI]2     

铜(Ⅱ)-三氮唑偶氮络合物与脱氧核糖核酸相互作用的电化学行为

运用电化学方法研究了铜（Ⅱ）－三氮唑偶氮（2－[2,3,5-三氮唑偶氮]-5－二甲氨基苯甲酸，TZAMB）络合物与脱氧核糖核酸（DAN）的相互作用。在pH2.5(0.05mol/L）邻苯二甲酸氢钾（PBS）缓冲溶液中，DNA与Cu(Ⅱ）－TZAMB络合物形成一种电惰性结合物，使Cu（Ⅱ）－TZAMB络合物的还原峰电流减小。通过循环伏安法、盐效应以及紫外－可见吸收谱证实了是由Cu(Ⅱ）－TZAMB络合物与DNA形成一种插入式的电惰性结合物而使其峰电流下降。根据这种峰电流下降可以测定DNA，测定结果令人满意。     

固固相反应合成牛磺酸水杨醛钾与锑、铋的配合物

合成了牛磺酸水杨醛钾,并采用室温固固相反应法合成了牛磺酸水杨醛钾与三氯化锑和三氯化铋的配合物,其组成为:K2MC18H20O8N2S2 (M = Sb, Bi)。两种配合物的晶体结构均属于单斜晶系,锑配合物的晶胞参数为:a = 1.2869 nm, b = 1.7636 nm, c = 1.9917 nm, β= 93.79埃活榕浜衔锏木О问篴 = 1.4770 nm, b = 2.0334 nm, c = 2.0149 nm, β= 94.05。红外光谱表明N、Cl原子参与了配位,中心离子的配位数为5。