电荷转移配合物的室温固相合成与性质研究

首次报道用室温固相反应法合成了一种有机 -多金属氧酸盐电荷转移配合物 (H2 quin) 3(PW12 O4 0 )· 4Hquin,用元素分析、红外、紫外、固体电子光谱、XRD、TG-DTA、极谱、伏安、ESR和变温磁化率等手段对其进行了研究 ,确定了该配合物的组成与结构。红外、紫外、固体电子光谱研究表明 8-羟基喹啉与杂多阴离子之间发生了电荷转移反应 ,ESR和极谱、伏安研究结果证明配合物中杂多阴离子发生了单电子还原反应 ,生成了混合价化合物。     

有机荧光材料研究进展

对三类主要的有机荧光材料－－具刚性结构的芳香稠环化合物，具共轭结构的分子内电荷转移化合物及某些金属配合物尤其是稀土金属配合物近二十年来的研究与应用进行了综述，引用文献48篇。     

含Dawson结构杂多钨磷(砷)酸电荷转移配合物的合成、结构与性质

近年来,有机多金属氧酸盐电荷转移配合物由于有特殊的光、电、磁性质在催化、功能材料及药物化学等领域受到研究者的广泛关注［１］。自从１９８８年法国的Ｌ．Ｏｕａｈａｂ［２］首次报道（ＴＴＦ）６ＰＷ１２Ｏ４０（Ｅｔ４Ｎ）２的合成以来,已见报道的多金属氧酸盐仅限于ＡｎｄｅｒｓｏｎＥｖａｎｓｅ、ｌｉｎｄｑｕｉｓｔ和Ｋｅｇｇｉｎ结构的多阴离子,对它们功能性质的系统研究也未见文献报道。为了研究阴离子的大小和形状对标题化合物功能性质的影响,作者在以前工作的基础上［３,４］,首次以Ｄａｗｓｏｎ结构杂多钨磷（砷）…     

有机-无机杂化材料[Na2(H2O)4]2[γ-Mo8O26·(Gly-Gly)2]·4H2O的合成及晶体结构

多金属氧酸盐因其独特的结构而具有较高的抗肿瘤及抗病毒活性,蛋白质和肽是氨基酸的聚合体,氨基酸侧链官能团能与多金属氧酸盐形成新型配合物.了解氨基酸和肽与多金属氧酸盐的相互作用对于深入研究多金属氧酸盐抗肿瘤及抗病毒机理很有意义.我们曾报道了赖氨酸、丙氨酸及甘氨酸二肽与钼磷酸所形成化合物的晶体结构.     

过渡金属配合物连接的多金属钒酸盐[Co(o-phen)]V2O6·H2O的水热合成和晶体结构

多金属氧酸盐 ( POMs)由于结构新奇 ,物理性能优异 ,在催化、医药、材料和光化学等领域有应用前景 ,而受到人们广泛关注 [1～ 8] .近年来 ,水热技术和有机指导剂的引入促进了 POMs的有机 -无机杂化材料如 [N( CH3) 4]5V18O4 6 [2 ]和 [V4 O10 ( phen) 2 ][3]等研究的迅速发展 .以上化合物多数仅以有机胺为抗衡离子或直接配位连接到无机骨架上 .而以过渡金属配合物为结构导向剂的合成策略 ,最近才引起人们的重视[9～ 11] .本文以钒酸盐 -过渡金属配合物作为研究体系 ,在水热条件下合成了一种未见文献报道的由新型过渡金属配合物连接的…     

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.     

氨基酸-多金属氧酸盐电荷转移配合物的固相法合成及表征

多金属氧酸盐是一类纳米级金属-氧多核配合物,可通过变换抗衡阳离子、杂原子、配原子等方法从原子、分子水平上进行物理或化学修饰,与不同的有机分子结合后可以获得具有特定功能和性质的化合物.     

尿素与Keggin结构磷钼酸电荷转移盐的合成与表征

在水中合成了两种新的有机 金属氧酸盐电荷转移配合物H3 PMo12 O4 0 ·4.5CO(NH2 ) 2 ·2 .5H2 O和H3 PMo12O4 0 ·12CO (NH2 ) 2 ,用IR、UV、TG、XRD及元素分析对其进行了表征。结果表明两种化合物中均存在[(H2 N) 2 COH]+ ,阴离子保持Keggin结构 ,但Keggin结构由于尿素的有机给体作用发生了不同程度的畸变。H3 PMo12 O4 0 ·4.5CO(NH2 ) 2 ·2 .5H2 O在固态 ,H3 PMo12 O4 0 ·12CO(NH2 ) 2 的水溶液具有光致变色效应     

稀土对K10H3[Y(SiW11O39)2]的多元渗及导电性

用降解法合成了具有Keggin结构的钇钨硅多金属氧酸盐, 以化学分析、 TG曲线和ICP确定通式为K10H3[Y(SiW11O39)2]. 利用IR、 183W-NMR等手段对配合物的结构进行了表征和研究, 结果表明配合物具有Keggin结构. TG-DTA分析表明配合物在400～450 ℃范围内仍不分解. 对配合物进行了化学热扩渗稀土的实验. 经ICP和XPS测试表明微量稀土元素可以渗入到配合物的表、界面乃至体相, 同时用四探针法和交流阻抗谱测试了不同温度下的电导率, 扩渗后样品的电导率σ=1.935×10-2 S*cm-1, 比扩渗前提高约105倍, 且随温度的升高, 导电性增强, 有望成为具有实际应用的多金属氧酸盐型固体电解质.     

有机电致发光红色发光材料研究进展*

本文总结了近年来有机金属配合物、分子内电荷转移化合物、稠环芳香类化合物以及齐聚物等几类有机电致发光红色发光材料的研究进展,详细介绍了它们在有机电致发光器件中的应用,并对有机电致发光红色发光材料未来的研究方向作了展望.     

TD-DFT Study on the Excited-State Hydrogen Bonding of the p-Cresol–NH3–H2O Complex

In this work, the time-dependent density functional theory (TD-DFT) method was used to study the electronic excited-state dynamics of the hydrogen-bonded p-Cresol–NH₃–H₂O complex. The intermolecular hydrogen bonds O₁–H₁···N and C–O₁···H₂ were demonstrated by the optimized geometric structure of the hydrogen-bonded p-Cresol–NH₃–H₂O complex. The infrared spectra (IR spectra) of the hydrogen-bonded p-Cresol–NH₃–H₂O complex in the ground and excited states were also calculated by using the density functional theory (DFT) and TD-DFT methods. It is demonstrated that hydrogen bond O₁–H₁···N can be strengthened while hydrogen bond C–O₁···H₂ is weakened upon photoexcitation to the S₁ state. The significant changes of the hydrogen bond from the calculated bond lengths in different electronic states can be observed. In addition, the spectral shifts of the stretching vibrational mode of the hydrogen-bonded O–H group in different electronic states are accounted for the hydrogen bond changes in the S₁ state too.     

Dinuclear Cobalt(III) Complexes Showing a Co2O2 Metallacycle

The heptadentate Schiff base H₃L reacts with cobalt(II) acetate in methanol to form the discrete dinuclear complex Co₂L(OAc)₂(OMe)(H₂O)₂ ( 1 ·2H₂O). The reaction of 1 ·2H₂O with NMe₄OH·5H₂O in methanol gives rise to displacement of the acetate by methanolate groups, yielding Co₂L(OMe)₃(H₂O) ( 2 ·1H₂O). Recrystallizations of the Schiff base, 1 ·2H₂O and 2 ·H₂O in different solvents, produce single crystals of H₃L, 1 ·2.5H₂O and 2 ·2MeOH, respectively. The crystal structures of 1 ·2.5H₂O and 2 ·2MeOH show the cobalt atoms double bridged by and endogenous phenol oxygen atom and an exogenous methanolate oxygen donor, giving rise to Co₂O₂ cores with Co···Co distances of ca. 2.87 Å.     

Synthesis and application of a new copper(II) complex containing oflx and leof

Two new copper(II) complexes of [Cu(Ofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O and [Cu(Levofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O were obtained and their structures were studies. Both ligands and complexes were assayed against gram-positive and gram-negative bacteria by the in vitro doubling dilutions method. The inhibitory effect of the ligands and complexes on the leukemia HL-60 cell line were measured with the MTT assay method and the liver cancer HePG-2 cell line measured by the SRB method. The results indicated that the complexes have stronger inhibitory effect on HL-60 than on HePG-2. The complex [Cu(Levofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O (I) has stronger effect on HL-60 than the complex (Cu(Ofloxacin)(phen)(H₂O)] · (NO₃) · 2H₂O (II). The text was submitted by the authors in English.     

Preparation of glycerol plasticized chitosan films using AlCl3·6H2O as the solvent: optical,crystalline, mechanical and barrier properties

Chitosan films plasticized with the complex of AlCl₃·6H₂O and glycerol were prepared by using AlCl₃·6H₂O as the solvent. The effect of AlCl₃·6H₂O and glycerol complex with Chitosan was studied by SEM, XRD, TGA, and tensile testing. The complex would increase the water resistance and destroy the crystals of chitosan film. The TGA results proved that the chitosan film plasticized with the complex showed higher thermal stability at the temperature below 200?°C than pure chitosan film. With the addition of the complex of AlCl₃·6H₂O and glycerol, the tensile strength of chitosan film decreased and the elongation at break increased.     

Luminescence and magnetic properties of mixed-ligand europium trifluoroacetates

The luminescence and magnetic properties of mixed-ligand europium trifluoroacetates with nitrogen- and phosphorus-containing neutral ligands [Eu(TFA)₃ · 3H₂O]₂ and Eu(TFA)₃ · 2D · nH₂O were studied (here TFA is the trifluoroacetic acid anion, and D is Phen (1,10-phenanthroline), n = 1; DMF (dimethylformamide), n = 1; or TPPO (triphenylphosphine oxide), n = 3). The molar magnetic susceptibility increased in the series of complex compounds Eu(TFA)₃ · 2Phen · H₂O < [Eu(TFA)₃ · 3H₂O]₂ < Eu(TFA)₃ · 2DMF · H₂O < Eu(TFA)₃ · 2TPPO · 3H₂O. Correlations were found between the luminescent and magnetic characteristics of the complex compounds.     

Antimicrobial mechanism of copper (II) 1,10-phenanthroline and 2,2′-bipyridyl complex on bacterial and fungal pathogens

Copper based metallo drugs were prepared and their antibacterial, antifungal, molecular mechanism of [Cu(SAla)Phen]·H₂O and [Cu(SAla)bpy]·H₂O complexes were investigated. The [Cu(SAla)Phen]·H₂O and [Cu(SAla)bpy]·H₂O were derived from the Schiff base alanine salicylaldehyde. [Cu(SAla)Phen]·H₂O showed noteworthy antibacterial and antifungal activity than the [Cu(SAla)bpy]·H₂O and ligand alanine, salicylaldehyde. The [Cu(SAla)Phen]·H₂O complex showed significant antibacterial activity against Salmonella typhi, Staphylococcus aureus, Salmonella paratyphi and the antifungal activity against Candida albicans and Cryptococcus neoformans in well diffusion assay. The mode of action of copper (II) complex was analyzed by DNA cleavage activity and in silico molecular docking. The present findings provide important insight into the molecular mechanism of copper (II) complexes in susceptible bacterial and fungal pathogens. These results collectively support the use of [Cu(SAla)Phen]·H₂O complex as a suitable drug to treat bacterial and fungal infections.     

The effect of ligand basicity on the thermal stability of heterodinuclear NiII–ZnII complexes

Four complexes of the nuclear structure Ni^II–Zn^II were prepared with bis-N,N′-(salicylidene)-1,3-propanediamine (LH₂), bis-N,N′-(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH₂) and the reduced derivatives of these Schiff bases, bis-N,N′-(2-hydroxybenzyl)-1,3-propanediamine (L^HH₂), bis-N,N′-(2-hydroxybenzyl)-2,2′-dimethyl-1,3-propanediamine (LDM^HH₂). The complexes were characterized using IR spectroscopy, elemental analysis and thermogravimetric methods. The stoichiometry of the complex molecules were found to be NiL·ZnCl₂·(DMF)₂, NiLDM·ZnCl₂·(DMF)₂, NiL^H·ZnCl₂·(DMF)₂ and NiLDM^H·ZnCl₂·(DMF)₂. The molecular models of the complexes prepared with the reduced Schiff bases were determined according to the X-ray diffraction method. It is seen that in these complexes Ni(II) is in octahedral and Zn(II) is in tetrahedral coordination sphere. Ni(II) ion is coordinated between two nitrogen and two oxygen donors of the ligand and oxygen donors of the two DMF molecules. Zn(II) ion on the other hand is coordinated between two oxygen of the organic ligand forming two μ bonds. It also coordinates two Cl ions. The thermogravimetric analysis showed that the complex NiLDM^H·ZnCl₂·(DMF)₂ containing methyl groups is more stable than the other complex NiL^H·ZnCl₂·(DMF)₂ containing reduced Schiff base. The coordinative DMF molecules in NiLDM^H·ZnCl₂·(DMF)₂ were thermally cleaved. However, the cleavage of DMF molecules NiL^H·ZnCl₂·(DMF)₂ resulted in the thermal degradation of the complex. In order to explain the TG data of the ligands were titrated in non-aqueous medium and their basicity strengths were determined. It was found that the basicity of the ligands containing two methyl groups were stronger. It is understood that the two methyl groups increase the negative charge density on nitrogen causing an increase in complex stability.     

Complexing between orthoperiodic acid and periodate ion in nitric acid solutions

Preparative synthesis techniques have been developed for four complex salts (Rb[H₄IO₆ · H₅IO₆], Cs[H₄IO₆ · H₅IO₆], Cs[H₄IO₆ · H₅IO₆ · 0.5H₂O], and 2CsNO₃ · HNO₃ · H₅IO₆). In the Cs(Rb)NO₃-H₅IO₆-HNO₃-H₂O systems, the starting component ratios, temperature schedules, and solvent-evaporation (H₂O + HNO₃) parameters have been determined to ensure the crystallization of the said compounds in individual states. For complex 2CsNO₃ · HNO₃ · H₅IO₆, solid-phase synthesis has also been developed. Highly water-sensitive Cs[H₄IO₆ · H₅IO₆] in the presence of water vapor converts to Cs[H₄IO₆ · H₅IO₆ · 0.5H₂O].     

Water-soluble cobalt complexes with 1-hydroxyethylydenediphosphonic acid and 2-aminoethanol

The reaction of an aqueous suspension of basic cobalt carbonate CoCO₃·4Co(OH)₂·3H₂O with equimolar amount or two-fold excess of 1-hydroxyethylydenediphosphonic acid (H₄L) has yielded crystalline CoH₂L and amorphous Co(H₃L)₂ products, respectively. The interaction of poorly soluble CoH₂L complex with 2-aminoethanol has resulted in the formation of amorphous water-soluble CoH₂L·H₂NCH₂CH₂OH·6Н₂О complex; the latter loses 5 water molecules at heating and is converted into CoH₂L·H₂NCH₂CH₂OH·Н₂О. The study of agrochemical effects of Co(H₃L)₂ and CoH₂L·H₂NCH₂CH₂OH·6Н₂О has revealed their advantage over the conventional salt form (cobalt sulfate) reflected in the reduced phytotoxicity of the element. The prepared compound containing 2-aminoethanol (solubility promotor) has revealed better performance.     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.