超细粉体二硫纶·取代菲咯啉铁(Ⅱ)配合物的光敏性研究

报道了新近合成的二硫纶·取代菲咯啉铁 (Ⅱ )配合物FeLL′(L =mnt2 - ,1 ,2 二氰基乙烯 1 ,2 二硫醇离子 ,L′ =phen 5,6 dione,1 ,1 0 菲咯啉 5,6 二酮 ;5 NO2 phen ,5 硝基 1 ,1 0 菲咯啉 )的电子吸收光谱、电子发射光谱及对CdS的光敏性 ,研究了FeLL′对CdS的光敏化作用与其电子光谱间的关系     

[Cd（SS）（NN）]配合物掺杂CdS的光-电转换特性

本文报道了配合物[Cd(SS)(NN)](SS=mnt2-,1,2-二氰基乙烯-1,2-二硫醇离子.NN=phen-5,6-dione,1,10-菲咯啉-5,6-二酮)的合成.探讨了Cd(SS)(NN)的电子吸收光谱和发射光谱。研究了掺杂有配合物Cd(SS)(NN)的CdS复合膜的光-电转换特性。     

一种功能型混配镍配合物的溶剂化显色特性与结构关系

详细报道了新近合成的二氰基二硫纶·邻菲罗啉二酮合镍配合物Ni(mnt) (phen - 5,6-dione) (mnt2 - ∶1,2 -dicyano - 1,2 -ethylenedithiolateormaleonitriledithiolate ;phen - 5,6-dione∶1,10 -phenanthroline - 5,6-dione)的电子吸收光谱 ,着重研究了可见光区中的溶剂化显色吸收带在相关分子轨道能级图中的对应跃迁关系 ,探讨了LL′CT的本质和感光氧化现象。     

超细粉体二氰基二硫纶·5-硝基菲咯啉铜(Ⅱ)配合物的结构与磁性

报导了新近合成的超细粉体二氰基二硫纶·5 -硝基菲咯啉铜 (Ⅱ )配合物CuLL′(L =mnt2 -,1,2 -dicyano_1,2_ethylenedithiolate ;L′ =5 -NO2 -phen ,5_nitri- 1,10 -phenanthroline)的质谱、透射电镜、变温磁化率和电子顺磁共振波谱表征结果 .发现标题配合物是纳米级 (颗粒直径约 30nm)的微晶粉体 ,具有显著的顺磁性 ,形成四配位的高自旋态构型 .探讨了这种配合物磁学特性与结构的关系 .     

7，7，8，8－四氰基对苯醌二甲烷与邻菲咯啉稀土配合物的合成和表征

７，７，８，８－四氰基对苯醌二甲烷与邻菲咯啉稀土配合物的合成和表征张明杰，聂玉敏，史志勤，张文胜，梁惠来（天津大学化学系天津３０００７２）（天津大学电子工程系天津）关键词四氰基对苯酮二甲烷，邻菲咯啉，镧配合物，钕配合物，合成７，７，８，８－四氰基对苯...     

1,10-邻菲咯啉-5,6-二酮制备反应中副产物的形成与控制

由1,10-邻菲咯啉合成1,10-邻菲咯啉-5,6-二酮反应的副产物的形成与控制研究表明,1,10-邻菲咯啉在5,6位二酮化反应中的副反应产物及主产物分离时产生的副产物均为4,5-二氮杂芴-9-酮,二酮化反应条件(包括作为氧化剂的强混合酸H2SO4/HNO3的加入量、时间和温度)和主产物分离时体系的酸度对副产物的形成有重要影响,优化了二酮化反应条件和产物分离时的体系pH控制范围。在此优化条件下,可有效控制副产物的形成,使主产物1,10-邻菲咯啉-5,6-二酮的收率达到92%以上。     

1,2′-二氰基-1,2′-二硫烯镍(II)离子对配合物的合成及晶体结构和弱相互作用

二氰基二硫烯(mnt和i-mnt)的金属配合物因其结构独特并呈现出特殊的光、电和磁学等性质,多年来引起科学家们广泛的关注[1-2].特别是在含Ni(mnt)2阴离子的离子对配合物中,功能阳离子的大小和构型改变可以导致Ni(mnt)2阴离子的重叠模式和堆积方式的变化,从而影响这类配合物的物理性能[3-5].为进一步探索取代苄基吡啶鎓离子中取代基团对1,2′-二氰基-1,2′-二硫烯镍配合物的结构的影响,我们在以前工作的基础上[6-8],合成了1种新的1,2′-二氰基-1,2′-二硫镍(II)离子对配合物[Bz(Me)Py]2[Ni(mnt)2],用元素分析、红外光谱和X-射线衍射表征了其组成和结构,讨论了配合物晶体中弱的相互作用.     

一种1, 10-菲啰啉-5, 6-二酮及其单肟的高效合成方法

1,10-菲啰啉-5,6-二酮(2)与1,10-菲啰啉-5,6-二酮单肟(3)作为稠杂环共轭配体,既具有良好的配位特性,又是重要的有机合成反应中间体.由化合物2和它的衍生物与金属离子形成的配合物可以用于抗肿瘤药物、DNA探针、非线性光学材料、超分子组装分子骨架、自旋交叉配合物等许多领域.化合物3则用于有机光致变色化合物螺噁嗪的合成.     

二氯·菲咯啉二酮混配金属锰(Ⅱ)、铁(Ⅱ)、钴(Ⅱ)配合物的合成与性质

以MCl2和配体L(L=1,10 菲咯啉 5,6 二酮)为原料,合成了标题配合物MLCl2,M=Mn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ),并经元素分析、电子吸收光谱、红外光谱表征.三者均为四配位的电中性配合物,热稳定性高于500K,易溶于DMF、DMSO和吡啶,可溶于二氯乙烷、乙醇和水.它们在DMSO、DMF中于350nm和310nm附近显示出强的M→L荷移跃迁.     

大空间位阻的2,9-双噻吩-1,10-菲咯啉-5,6-二酮铜(Ⅱ)配合物

基于1,10-菲咯啉-5,6-二酮2,9位双噻吩的扩展策略,设计合成了2个化合物1和2。有趣的是,在大位阻双齿螯合配体2的配位化学研究中发现,只有铜( Ⅱ)离子生成了稳定的配合物3·H2O。此外,对2,2·CHCl3和3·H2O的X-射线单晶结构研究表明,为了克服空间位阻以满足中心铜( Ⅱ)离子的配位构型要求,1,10-菲咯啉-5,6-二酮及其2,9位取代的2个噻吩环之间的二面角分别从自由配体中的1.9(2)°、5.2(6)°和25.3(3)°、34.9(3)°增加到了铜( Ⅱ)配合物中的5.6(2)°、6.5(6)°和27.2(3)°、38.2(3)°。     

Synthesis,characterization, and immobilization of nickel(II) tetradentate Schiff-base complexes on clay as heterogeneous catalysts for the oxidation of cyclooctene

Nickel(II) tetradentate Schiff-base complexes of N,N′-(bis(pyridin-2-yl)formylidene)ethane-1,2-diamine (L1), N,N′-(bis(pyridin-2-yl)formylidene)cyclohexane-1,2-diamine (L2), N,N′-(bis(pyridin-2-yl)formylidene)benzene-1,2-diamine (L3), N,N′-(bis(pyridin-2-yl)formylidene)meso-stilben-1,2-diamine (L4), and N,N′-(bis(pyridin-2-yl)formylidene)propane-1,3-diamine (L5) were synthesized, characterized, and immobilized on sodium montmorillonite. The complexes were characterized by IR spectroscopy, diffuse reflectance spectra (DRS), and atomic absorption spectroscopy (AAS). IR and DRS data of the heterogeneous catalysts show that the Ni(II) complexes were physically entrapped within the sodium montmorillonite clay. The supported complexes show good catalytic activity for the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxygen source in acetonitrile. The Ni-catalyzed oxidation proceeds with 62.3% selectivity for epoxidation with 69% conversion for supported [Ni(L5)].     

ESI-MS studies of mixed-ligand Fe(II) complexes containing 1,10-phenanthroline and 1,10-phenanthroline-5,6-dione as ligands

In order to monitor the progression of the synthesis and the separation of novel mixed-ligand iron complexes containing 1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, and NCS- as ligands all products were mass analyzed by electrospray ionization ion trap MS/MS. The spectra of methanol (MeOH), acetonitrile (ACN), water, and ethanol (EtOH) solutions were collected and the results were compared. It was detected under applied electrospray ionization mass spectrometry (ESI-MS) conditions that MeOH, water, and EtOH formed solvent clusters around the free or complexed 1,10-phenanthroline-5,6-dione. Owing to the solvent-ligand hydrogen-bond formation, the solvent-ligand clusters were formed in the polar protic solvents. The number of protic solvent molecules per complex ion in cluster depended on the number of 1,10-phenanthroline-5,6-dione ligands in the complex ion. Unlike MeOH, EtOH, or water, ACN was not involved in the formation of the solvent clusters with the iron complexes containing 1,10-phenanthroline-5,6-dione as ligand. We also showed that the NCS- group under certain solvent conditions served as a bidentate ligand.     

Rhodium-catalyzed asymmetric hydroformylation of vinylarenes with novel chiral P,N-ligands derived from 1,2:5,6-di-O-cyclohexylidene-d-mannitol

Several new chiral P,N-ligands were prepared from 1,2:5,6-di-O-cyclohexylidene-d-mannitol, 1,1′-binaphthol, and phenyl isocyanate derivatives. Their Rh(I) complexes were applied as catalyst precursors in the asymmetric hydroformylation of vinylarenes. The steric and electronic properties of the phenylcarbamate substituents and the chiral binaphthyl moiety showed remarkable effects on the enantioselectivity and regioselectivity of the reaction. The matching combination of phenylcarbamate and the binaphthyl moiety of the ligand 1,2:5,6-di-O-cyclohexylidene-3-phenylcarbamate-4-[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitol gave 50% ee and an 89/11 b/n ratio (branch-to-normal ratio). A synergic effect between the chiralities of mannitol and the binaphthol moieties was observed. Hydroformylation of the styrene gave the product in 75% ee when 1,2:5,6-di-O-cyclohexylidene-3,4-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitol was used as the chiral ligand.     

Condensed isoquinolines. 35*. Synthesis and reactions of 4h-thieno[3′,4′:5,6]pyrimido-[1,2-<Emphasis Type="Italic">b</Emphasis>]isoquinoline-4,11(5H)-dione

Derivatives of the previously unknown tetracyclic system 4H-thieno[3′,4′:5,6]pyrimido[1,2-b]iso-quinoline-4,11(5H)-dione have been synthesized. A comparison of the spectral characteristics and the biological activities of these compounds has been carried out, and also of their positional isomers and benzene isosteres. The differences, associated with the position of the sulfur atom, are most reflected in their electronic spectra.     

Synthesis,characterization and fluorescence spectra of mononuclear Zn(II), Cd(II) and Hg(II) complexes with 1,10-phenanthroline-5,6-dione ligand

The mononuclear complexes of Zn(II), Cd(II) and Hg(II), [Zn(phen-dione)Cl₂], [Cd(phen-dione)Cl₂] and [Hg(phen-dione)Cl₂], where phen-dione?=?1,10-phenanthroline-5,6-dione, have been synthesized and characterized by elemental analysis and IR, ¹H?NMR and electronic absorption spectroscopies. The ν(C=O) of coordinated phen-dione ligands in these complexes shows that the phen-dione is not coordinated to metal ion from its C=O sites. Electronic spectra of the complexes show two absorption bands for intraligand transitions. These absorption bands show dependence on the dielectric constant of solvents. These complexes exhibit an intense fluorescence band around 545?nm in DMSO when the excitation wavelengths are 200?nm at room temperature.     

Synthesis of novel spiro-fused pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidines

New pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidines, with an associated spiro-3,3′-oxindole attachment, were prepared by three-component combinations of 5,6-dihydro-4H-pyrrolo[3,2,1-ij]quinoline-1,2-dione with a pair of reactants chosen from a pyrazol-5-one, a pyrazole-5-amine, a barbituric acid, or a 6-aminouracil.