草酰胺桥联大环二羰四胺铜(Ⅱ)-钴(Ⅱ)异双核配合物的合成、结构、表征和电化学性质

合成了一种具有草酰胺桥联大环二羰四胺结构的 Cu( ) -Co( )异双核配合物 ,用红外光谱、电子光谱、摩尔电导、热重分析、室温磁矩、循环伏安等对其进行了表征 .初步推定 Cu( ) -Co( )异双核配合物具有草酰胺桥联大环二羰四胺结构 .室温磁矩测定表明 ,通过草酰胺桥联配体金属离子间有一定的反铁磁性自旋偶合作用 .循环伏安法测定了配合物的半波电位 ,实验表明 ,此类配合物能够稳定高价态 Cu( ) ,外延桥基配位对大环内腔 Cu( )离子的氧化还原过程无影响 .单核配合物 X射线晶体衍射研究表明 ,其为单斜晶系 ,空间群 P2 1 /c,a=0 .73 861 (1 5 ) nm,b=2 .1 2 1 1 (4 ) nm,c=0 .95 2 5 0 (1 9) nm,β=94.70 (3 )°,R1 =0 .0 5 1 3 ,w R2 =0 .1 1 77,Z=4.Cu( )处于大环四胺平面正方中心上方 0 .0 3 nm,并具有外延草酰胺桥     

草酰胺桥联大环二羰四胺铜(Ⅱ)-钴(Ⅱ)异双核配合物的合成、结构、表征和电化学性质

合成了一种具有草酰胺桥联大环二羰四胺结构的Cu(Ⅱ)-Co(Ⅱ)异双核配合物,用红外光谱、电子光谱、摩尔电导、热重分析、室温磁矩、循环伏安等对其进行了表征. 初步推定Cu(Ⅱ)-Co(Ⅱ)异双核配合物具有草酰胺桥联大环二羰四胺结构. 室温磁矩测定表明,通过草酰胺桥联配体金属离子间有一定的反铁磁性自旋偶合作用. 循环伏安法测定了配合物的半波电位,实验表明,此类配合物能够稳定高价态Cu(Ⅲ),外延桥基配位对大环内腔Cu(Ⅱ)离子的氧化还原过程无影响. 单核配合物X射线晶体衍射研究表明,其为单斜晶系,空间群P21/c,a=0.738 61(15) nm,b=2.121 1(4) nm,c=0.952 50(19) nm,β=94.70(3)°,R1=0.051 3,wR2=0.117 7,Z=4. Cu(Ⅱ)处于大环四胺平面正方中心上方0.03 nm,并具有外延草酰胺桥.     

Schiff碱Ni(Ⅱ)单核及Ni(Ⅱ)-Fe(Ⅲ)异双核配合物的合成表征及电化学性质

合成了二(3 羧基水杨醛叉)缩1,3 丙二胺(TS)Schiff碱配体的Ni(Ⅱ)单核配合物Na2Ni(TS)·2H2O和Ni(Ⅱ) Fe(Ⅲ)异双核配合物NiFe(TS)Cl·2.5H2O 用元素分析、摩尔电导、IR光谱、UV光谱及差热分析对配合物的组成和结构进行了表征 采用循环伏安法研究了配合物的电化学性质,研究表明:由于第二金属离子的配位增强了内部镍离子的电化学稳定性     

Cu(Ⅱ)-VO(Ⅱ)异双核Schiff碱配合物的合成、电化学和磁学性质

Cu(Ⅱ)-VO(Ⅱ)异双核Schiff碱配合物的合成、电化学和磁学性质;循环伏安法     

两种不对称草酰胺桥联双核铜(Ⅱ)配合物的合成及电化学性质

合成了两种新型草酰胺桥联双核铜配合物 ,并以元素分析、红外光谱、电子光谱、摩尔电导、热重分析和室温磁矩对所合成铜配合物进行表征 ,推定新合成的双核铜配合物具有草酰胺桥联结构 .采用循环伏安法测定了双核配合物的氧化还原电位 ,表明两种配合物均显示一个单电子还原过程 .     

三乙烯四胺-咪唑的非对称异双核配合物的合成及电化学性质

许多过渡金属含氮配合物具有抗菌、抗癌、抗病毒等生物活性,受到人们的广泛重视[1]。其中三乙烯四胺(trien)是有效的生成单双核配合物的含氮配体,已设计合成了一系列过渡金属及稀土金属的均双核和异双核配合物,并进行了结构表征和性能研究[2]。对于其异双核咪唑桥联配合物,前文     

含烷氧基桥的双核Ni(Ⅱ)配合物的合成、表征和磁性

以Ｎ－氧化吡啶－２－甲醛和１，３－二氨－２－丙醇合成了含烷氧基桥的双Ｓｃｈｉｆ碱双核配体及其五个镍的双核配合物。通过元素分析、摩尔电导、红外光谱、ＴＧ对配合物进行了表征，并对其中两个配合物中Ｎｉ（Ⅱ）－Ｎｉ（Ⅱ）间磁交换作用进行了研究。     

一个新型碗状双核配合物的合成及结构表征

采用挥发法，在无水条件下合成了一个新型具有碗状结构的双核稀土金属配合物：[Y₂(L)(HL)(NO₃)₆(HCOO)]·3CH₃OH[L=1，3，5-三(1-咪唑基-亚甲基)-2，4，6-三甲基苯] (1)。并通过元素分析、FT-IR、电喷雾质谱及X-射线单晶衍射对其进行了表征。结构分析表明该化合物属于正交晶系，空间群为Pnnm，晶胞参数为a=1.952 42(15) nm，b=1.875 28(19) nm，c=1.682 25(15) nm，晶胞体积V=6.159 3(10) nm³，Z=4。在化合物1中，两个独立的Y(Ⅲ)均为九配位，并通过甲酸根桥联，而两个配体采用不同的构象作为二齿配体参与与Y(Ⅲ)的配位，一个为cis，cis，cis-构象，另一个为cis，trans，trans-构象。     

对-氢醌金属配合物：合成，结构及电化学性质

A new Chromium(Ⅲ) complex, [Cr(Hcah)(H₂O)₂]·2H₂O, where H₄cah=2-[N,N-bis(carboxymethyl)aminome-thyl] hydroquinone (H₄cah), has been synthesized and characterized using X-ray diffraction single crystal structure determination, IR and elemental analysis. The complex belongs monoclinic, space group P2₁/c, with a=0.792 05(4) nm, b=1.008 63(6) nm, c=1.920 40(10) nm, β=93.069(4)°, V=1.531 98(14) nm³, and Z=4. The cyclic voltametric analysis shows that the electron transfer in the electrode reaction is irreversible for Cr(Ⅲ)/Cr₂O₇^2- and Cr(Ⅲ)/Cr(Ⅱ) redox couples while reversible for process of interchange from p-Hydroquinone to p-semiquinones. CCDC: 666208.     

Synthesis, Crystal Structure and Electrochemical Studies of Two Novel Zn(II) Complexes of Phthalic Acid and Imidazole Derivatives

Two novel coordination polymers [Zn(pa)(vim)2]n (1) and [Zn(pa)(eim)2]n (2) (pa＝phthalic acid dianion, vim＝1-vinyl-1H-imidazole, eim＝1-ethyl-1H-imidazole) have been synthesized and their structures characterized by X-ray single crystal diffractometry and elemental analysis. Both of the complexes consist of [Zn(L)2] (L＝vim for 1; eim for 2) entities linked into polymeric zigzag chains along the crystallographic c-axis by bridging phthalate anions in the μ2-1,2 coordination mode. The coordination around each Zn(II) atom is tetrahedral. There are only van der Waals interactions between the chains in 1, while the three-dimensional network in 2 is assembled by C—H…O contacts. The electrochemical studies reveal that redoxes of Zn2+/Zn in complexes 1 and 2 are irreversible processes.     

二（1N-苄基-苯并咪唑）二氯合钴配合物的晶体结构、电化学和热稳定性能研究(英)

0IntroductionBenzimidazoleisaninterestingheterocyclicringbecauseitispresentinvariousnaturallyoccurringdrugs,suchasomeprazole,astemizoleandemedastinedifumarate[1].Theefficacyofsubstitutedbenzimida鄄zolesinthetreatmentofparasiticinfectionsiswellknown[2,3].B…     

Flavin Derivatives with Tailored Redox Properties: Synthesis,Characterization, and Electrochemical Behavior

This study establishes structure–property relationships for four synthetic flavin molecules as bioinspired redox mediators in electro‐ and photocatalysis applications. The studied flavin compounds were disubstituted with polar substituents at the N1 and N3 positions (alloxazine) or at the N3 and N10 positions (isoalloxazines). The electrochemical behavior of one such synthetic flavin analogue was examined in detail in aqueous solutions of varying pH in the range from 1 to 10. Cyclic voltammetry, used in conjunction with hydrodynamic (rotating disk electrode) voltammetry, showed quasi‐reversible behavior consistent with freely diffusing molecules and an overall global 2e^?, 2H⁺ proton‐coupled electron transfer scheme. UV/Vis spectroelectrochemical data was also employed to study the pH‐dependent electrochemical behavior of this derivative. Substituent effects on the redox behavior were compared and contrasted for all the four compounds, and visualized within a scatter plot framework to afford comparison with prior knowledge on mostly natural flavins in aqueous media. Finally, a preliminary assessment of one of the synthetic flavins was performed of its electrocatalytic activity toward dioxygen reduction as a prelude to further (quantitative) studies of both freely diffusing and tethered molecules on various electrode surfaces.     

RuNi双核配合物识别DNA的分子机理研究

RuNi异金属双核配合物Ru(phen)_2(phen-cyclam-Ni)~(4+)(1)(phen=1,10-邻菲咯啉;cyclam=1,4,8,11-四氮杂环十四烷)和Ru(bpy)_2(bpy-cyclam-Ni)~(4+)”(2)(bpy=2,2 ’-联吡啶)具有多种重要的性质和功能;为了阐明它们在体外抗艾滋病病毒(HIV-1)活性方面的分子机理,我们用多种手段研究了这些化合物与DNA的相互作用。 1 实验部分 配合物1和2根据文献合成。粘度测定用乌氏粘度计在Pipes 00缓冲液中于300.2℃下进行。紫外可见光谱用Varian DMS 200 UV-Vis分光光度计在室温下测定。DNA断裂活性的测定采用DYY-Ⅲ4型电泳仪,0.8％的琼脂糖凝胶,电泳缓冲液用05×TBE。对pBR322质粒DNA的断裂结果在紫外透射及反射仪上观察和照相,并用紫外薄层扫描法进行初步定量分析。 2 结果与讨论 2.1 粘度测定 当用配合物1对DNA(CT-DNA)溶液进行滴定时,其特性粘度有较明显的     

Electrochemical Synthesis and Characterization of Electroactive Conducting Polypyrrole Polymers

Conducting/electroactive polypyrrole polymers are synthesized electrochemically on glassy carbon in various electrolytes (counterions). The polymers' electroactivity is measured using cyclic voltammetry. The electrolytes are chloride, nitrate, p-toluene sulfonate, dodecyl sulfate, and dodecylbenzenesulfonate of sodium and potassium ferrocyanide. It is found that the electrolyte (dopant) markedly affects the redox behavior of the polypyrrole films.     

一种含二茂铁基的多枝状分子的合成、表征及其性质研究

采用新的方法合成了一种二茂铁衍生物——均三（二茂铁乙烯基）苯，通过元素分析、红外光谱、核磁共振氢谱、质谱、紫外可见光谱等对其进行了表征。用循环伏安法对其电化学性质进行了初步研究，用Z-扫描技术测试了它的非线性光学性能。结果表明，该化合物具有良好的电化学及非线性光学性质。     

Synthesis and Characterization of Conducting Copolymers of Thiophene Derivatives

Electrochemical copolymerizations of N¹,N²-bis(thiophen-3-ylmethylene)benzene-1,2-diamine (TMBD), 4-methyl-N¹,N²-bis (thiophen-3-ylmethylene)benzene-1,2-diamine (MTMBD) and 4-nitro-N¹,N²-bis(thiophen-3-ylmethylene)benzene-1,2-diamine (NTMBD) with 3,4-ethylenedioxy thiophene (EDOT) were carried out in CH₃CN/LiClO₄ (0.1 M) solvent–electrolyte couple via potentiodynamic electrolysis. The resulting copolymers were characterized by cyclic voltammetry (CV), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The conductivity measurements of copolymers and PEDOT were carried out by the four-probe technique.     

杂双核Rh(I)-Cr配合物催化乙炔氢甲酰化反应机理的密度泛函研究

用密度泛函B3LYP方法对杂双核(CO)4Cr(μ-PH2)2RhH(CO)(PH3)配合物催化乙炔氢甲酰化反应机理进行了详细研究. 对结合和解离机理所涉及中间体和过渡态的结构进行详细分析, 在此基础上阐明了金属铬的协同性. 计算结果表明解离机理占主导地位. 乙炔氢甲酰化反应的决速步骤为炔烃插入步骤, 在298.15 K和101.325 kPa下的活化自由能为73.72 kJ/mol. 乙炔插入和醛还原消除步骤均在热力学上不可逆. Cr(CO)4部分的引入并没有改变乙炔氢甲酰化反应机理. Rh与Cr间的d轨道相互作用在反应过程起重要作用.