环金属钌配合物的合成、结构多样性及氧化还原调控（英文）

环金属钌配合物具有良好的氧化还原和光物理性质,在诸多光电领域如染料敏化太阳能电池、电致变色、电子转移等方面具有重要应用.环金属钌配合物的合成方法主要包括"后期金属化"、"前期金属化"、"转金属化"三种方法.环金属配合物具有丰富的结构多样性.环金属配合物由环金属配体和辅基配体与金属螯合形成.环金属配体包括N^C、N^N^C、N^C^N和C^C^C-类型多齿配体.辅基配体主要包括吡啶、咪唑、三唑、嘧啶等杂环.碳-金属键的引入大大降低了钌配合物的氧化还原电位.通过改变环金属配体和辅基配体的结构,可以对金属的氧化还原电位进行有效调控.金属钌配合物的氧化还原电位对敏化电池的性能以及电子转移的过程具有重要的影响.     

系列2-苯基喹啉类铱配合物的合成及电化学发光性能研究

以4-甲氧羰基-2-苯基喹啉为环金属配体,N^N辅助配体为解离配体合成了一系列离子型环金属铱配合物.配合物的结构通过质谱、核磁进行了表征.配合物1还测试了其单晶结构.对配合物的紫外、磷光性质进行了表征,溶液状态下为红光发射,波长在610～620 nm之间,磷光寿命在133～496 ns之间,量子效率在0.7%～16.6%之间.铱配合物的电化学发光与23Ru(bpy)+有所不同,发光电位比23Ru(bpy)+要高,且大部分铱配合物在正负电位都能发光,最大发光强度是23Ru(bpy)+的三倍.     

环金属钌配合物的合成、结构多样性及氧化还原调控

环金属钌配合物具有良好的氧化还原和光物理性质,在诸多光电领域如染料敏化太阳能电池、电致变色、电子转移等方面具有重要应用。环金属钌配合物的合成方法主要包括“后期金属化”、“前期金属化”、“转金属化”三种方法。环金属配合物具有丰富的结构多样性。环金属配合物由环金属配体和辅基配体与金属螯合形成。环金属配体包括N^∧C、N^∧N^∧C、N^∧C^∧N和C^∧C^∧C-类型多齿配体。辅基配体主要包括吡啶、咪唑、三唑、嘧啶等杂环。碳-金属键的引入大大降低了钌配合物的氧化还原电位。通过改变环金属配体和辅基配体的结构,可以对金属的氧化还原电位进行有效调控。金属钌配合物的氧化还原电位对敏化电池的性能以及电子转移的过程具有重要的影响。     

N,N''-双(3-甲酰基-4-羟基苯甲酸甲酯)缩环己二胺Schiff碱过渡金属配合物的合成及表征

在N2气保护下,3-甲酰基-4-羟基苯甲酸甲酯与环己二胺在无水乙醇中缩合反应合成了新型的Schiff碱配体N,N'-双(3-甲酰基-4-羟基苯甲酸甲酯)缩环己二胺,收率为66.7%.该配体与四水合醋酸锰在无水乙醇中反应,并经空气氧化、氯化锂处理得到Mn3+配合物;与三氯化铁、氯化镍在无水乙醇中配位分别得到Fe3+、Ni2+配合物.并通过红外光谱、核磁共振、元素分析等测试方法对配体和配合物结构进行了表征.     

1-苯基-3-甲基-4-萘乙酰基-吡唑啉酮-5 (PMNAP)缩2-氨基苯并咪唑(2-AB)席夫碱及其过渡金属配合物的合成、光谱表征与质谱鉴定

在非水溶剂中合成出一种新型席夫碱试剂(H2L): 1-苯基-3-甲基-4-萘乙酰基-吡唑啉酮-5 (PMNAP)缩2-氨基苯并咪唑(2-AB)及其过渡金属铜、铅、镍和钴配合物. 由元素分析、综合滴定和质谱数据推测出配合物的组成为ML•H2O, 通过红外光谱、紫外光谱、热重谱和核磁共振氢谱对配体和配合物进行了结构表征, 同时建立了合成体系的液相色谱分离和质谱鉴定方法, 在线得到了配体共存的三种异构体和目标配合物及其相应的质谱信息. 综合各种分析结果显示: 配体在测试条件下以酮式和烯醇式结构共存, 配位时酮式可能转化为烯醇式结构, 按去质子的方式以吡唑啉酮环羟基和H2O上的两个O原子以及亚胺基上的N原子和苯并咪唑环上的含氢N原子与中心离子成键, 配合物的配位数为4.     

含三芳胺基的吡啶甲酸衍生物及其环金属铱配合物的合成与性能

通过Ullmann反应和Negishi偶联反应, 合成了一种含三芳胺功能基的吡啶-2-甲酸衍生物; 并以此为辅助配体、1-苯基异喹啉为环金属配体, 设计合成了一种新型环金属铱配合物. 该配合物的二氯甲烷溶液, 在391～461 nm范围呈现了强烈的金属-配体电荷转移(MLCT)电子跃迁吸收带; 其最大发光波长为609 nm. 与传统的二(1-苯基异喹啉)(吡啶-2-甲酸)合铱配合物相比, 设计的环金属铱配合物具有增强的MLCT电子跃迁吸收和低的氧化电位, 是一种有发展潜力的红色磷光材料.     

双Schiff碱过渡金属配合物的合成及对环己烯催化氧化性能的研究

Schiff碱及其配合物在治疗肿瘤、抗菌、仿生载氧等方面具有优异的性能,在催化领域中也表现出多种性质。本文合成了三种结构简单的Schiff碱配体以及它们的过渡金属配合物,并研究了其对环己烯的催化环氧化性能。配体的结构如下。     

邻氨基苯酚Schiff碱多核配合物的合成与表征

合成了3-羧基水杨醛缩邻氨基苯酚Sch iff碱及其三核铜,三核镍配合物.用质谱分析,核磁共振,红外光谱,元素分析对配体和配合物的结构进行了表征.磁性研究表明,这两种配合物的金属离子间均存在着较强的反铁磁性自旋交换相互作用.     

非平面分子内电荷转移离子配合物的合成及其光物理性质

以N-乙烯基咔唑三羰基铬为模板化合物, 选用丙烯基阳离子取代其中一个羰基配体, 合成了一种新型非平面分子内电荷转移有机金属配合物. 通过元素分析、红外、核磁共振确定了配合物的组成和结构, 电子吸收和荧光光谱结果表明配合物的光物理行为可通过配体取代调控．运用双光束前向简并四波混频(DFWM)的方法, 测试了配合物及配体的三阶非线性效应, 同时探讨了金属配位和配体取代对其的影响.     

N,N′-双(3-甲酰基-4-羟基苯甲酸甲酯)缩环己二胺Schiff碱过渡金属配合物的合成及表征

在N2气保护下,3-甲酰基-4-羟基苯甲酸甲酯与环己二胺在无水乙醇中缩合反应合成了新型的Schiff碱配体N,N′-双(3-甲酰基-4-羟基苯甲酸甲酯)缩环己二胺,收率为66.7%。该配体与四水合醋酸锰在无水乙醇中反应,并经空气氧化、氯化锂处理得到Mn3 配合物;与三氯化铁、氯化镍在无水乙醇中配位分别得到Fe3 、N i2 配合物。并通过红外光谱、核磁共振、元素分析等测试方法对配体和配合物结构进行了表征。     

过渡金属与华法灵配合物的合成和抗凝血作用研究

用过渡金属硝酸盐与华法灵钠在不同介质制备了金属配合物, 所试验的各种制备方法均可获得恒定组成的配合物NanML3•2H2O (L＝华法灵离子, n＝0, 1). 通过元素分析、红外光谱、摩尔电导、紫外光谱、热重和溶解性试验对配合物进行了表征. 抗凝血试验表明过渡金属华法灵配合物具有一定的抗凝血性质. 并对过渡金属华法灵、过渡金属水杨酸、稀土金属华法灵、稀土金属华法灵水杨酸配合物的抗凝血性质进行了比较.     

Transformation of 2-alkoxyimidate-1,10-phenanthroline metal (Mn, Co and Ni) chlorides from bis(2-cyano-1,10-phenanthroline) metal chlorides: Syntheses, characterizations and their catalytic behavior toward ethylene oligomerization

The 2-alkoxyimidate-1,10-phenanthroline complexes of manganese, cobalt and nickel have been synthesized by the reaction of 2-cyano-1,10-phenanthroline with metal dichloride in the corresponding alcohol. The metal complexes bearing two 2-cyano-1,10-phenanthrolines were isolated in non-protonic solvent as the coordination around metal core with two ligands and two chlorides. The alkoxyimidation of nitrile linked on ligand was speeded in forming the 2-alkoxyimidate-1,10-phenanthrolinyl metal complexes. All the complexes have been characterized by FT-IR spectra and elemental analysis, and some of their structures have also been confirmed by single-crystal X-ray diffraction analysis. All the metal complexes were evaluated in the catalytic oligomerization of ethylene with some alkylaluminums as co-catalyst; in which manganese complexes were less active, cobalt complexes showed low to moderate activities, and nickel complexes gave moderate to good activities.     

Vanadium(III) Complexes of Oxygen Donor Ligands; Their Synthesis,Spectral Characterization and Antimicrobial Studies

A new series of vanadium(III) complexes with oxygen donor ligands have been synthesized and characterized on the basis of elemental analysis, conductance, infra‐red spectroscopy, electronic spectral data and mass spectrometry. Thermal stabilities of the complexes and their kinetics were studied through thermogravimetric analysis. Estimation of vanadium in the complexes is carried out by ICP‐AES. Biological activities of the complexes 2 – 5 , 7 and 8 have also been tested against various bacteria and fungi.     

N-氧化吡啶-2-甲醛双希夫碱配合物的研究

本文合成了N-氧化吡啶-2-甲醛与乙二胺、1,2-丙二胺和邻苯二胺生成的双希夫碱,并合成了以它们为配体的十八个配合物。用元素分析,电导,磁化率,红外,紫外与可见光谱,差热一热重分析等方法对配合物进行了表征。     

Transition metal chelates: Synthesis,physicochemical, thermal,and biological studies

The transition metal complex of Mn(II), Co(II), Ni(II), Cu(II), Ti(III), Cr(III), Fe(III), Zr(IV), and UO₂(VI) ion with a Schiff’s base ligand derived from 2-hydroxy-[2-oxo-1,2-dihydro-3H-indol-3-ylidene]-benzohydrazide have been prepared. The complexes have been characterized by elemental analysis data, IR and electronic absorption spectra, magnetic moments, and thermogravimetric analysis data. The complexes of the 1: 1 metal-to-ligand stoichiometry have been formed. The physico-chemical data have suggested the octahedral geometry for all the complexes except for Cu(II); the Cu(II) complex has been square planar. Thermal analysis data of the ligand and its complexes have been analyzed, and the kinetic parameters have been determined using the Horowitz–Metzger method. According to the solid-state electrical conductivity measurements, the ligand and its complexes are semiconducting in nature. The antimicrobial activity of the ligand and the complexes towards E. coli, S. typhi, P. aeruginosa, and S. aureus has been tested by the disc diffusion method.     

Metal ion-directed synthesis of 16-membered tetraazamacrocyclic complexes and their physico-chemical studies

Complexes of Co(II), Ni(II), Cu(II) and Zn(II) containing macrocyclic tetradentate nitrogen donor (N4) ligand have been synthesized from the template condensation reaction between o-phthalaldehyde and o-phenylenediamine. The newly synthesized ligand and its complexes have been characterized on the basis of results of elemental analysis, molar conductance, magnetic susceptibility measurements, FT-IR, electronic, 1H FT NMR spectral data and Job's method. Their thermal behaviour has been studied by the thermogravimetric analysis. An octahedral geometry has been proposed for all of these complexes except the copper complexes, which show distorted octahedral geometry. The low conductivity data suggest their non-ionic nature. The biological activities of the metal complexes have also been studied against different bacteria.     

Synthesis, structure, and properties of the Cu(II) coordination compounds with the pyruvic acid nicotinoyl and isonicotinoyl hydrazones

New coordination compounds of Cu(II) and hydrazones of nicotinic and isonicotinic acids have been prepared. The complexes isolated have been studied by elemental analysis, thermogravimetric analysis, magnetic susceptibility measurements, IR, diffuse reflectance, and EXAFS spectroscopy. The geometry of the compounds has been determined and the type of the ligands coordination has been revealed. Antibacterial activity of the complexes has been studied.     

[Co(solv)<Subscript>6</Subscript>][B<Subscript>10</Subscript>H<Subscript>10</Subscript>] (solv = DMF and DMSO) for low-temperature synthesis of borides

The synthesis and structure of complexes [Co(solv)₆][B₁₀H₁₀] (solv = DMF and DMSO) have been reported. Both complexes have been prepared in a high yield by the reaction between cobalt(II) salts and closo-decaborates Cat₂[B₁₀H₁₀] in the corresponding solvent. The complexes have been characterized by elemental analysis, IR and UV spectroscopy, X-ray powder diffraction, and X-ray crystallography. The thermal properties of the compounds have been studied in the temperature range 20–600°C under argon. The conditions to form cobalt borides have been determined based on the results of thermal analysis, subsequent annealing of the complexes in various conditions, and analysis of IR spectra of the resulting thermolysis products.     

The spectral and magnetic properties of some chloro and bromo transition metal complexes of picolinic acid and a study of their performance as colouring materials for poly(vinyl chloride)

Complexes of picolinic acid with the chlorides and bromides of manganese(II), iron(II), cobalt(II), nickel(II) and copper(II) have been prepared. Spectral and magnetic studies have shown that the iron complexes have discrete octahedral structures while the other complexes have polymeric octahedral structures. The decomposition of the complexes was studied by thermogravimetry and differential thermal analysis. The performance of the complexes as colouring materials for poly(vinyl chloride) has also been investigated.     

1-苯基-3-甲基-七氟丁酰吡唑酮-5(PMHFP)及邻菲咯啉(phen)希土混配配合物的合成及性质研究

本文在乙醇中合成了PMHFP及phen与希土离子的三元配合物Ln(PMHFP)_3·phen(Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y).通过化学分析,元素分析及电导分析确定了配合物的组成;研究了配合物的紫外、红光光谱;借助于差热-热重分析仪研究了所有配合物的挥发性质,测定了它们各自的起始挥发温度,探讨了用于希土分析的可能性.