Bis[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(perchlorato‐κO)copper(II) bis­[bis­(methoxy­carbimido)amine‐κ2N,N′]bis­(methanol‐κO)copper(II) bis­(perchlorate) methanol disolvate

The title compound, [Cu(ClO₄)₂(C₄H₉N₃O₂)₂][Cu(C₄H₉N₃O₂)₂(CH₄O)₂](ClO₄)₂·2CH₃OH, comprises two independent Cu^II species lying on different inversion sites. In the Cu complexes, a distorted octa­hedral geometry arises (from basic square‐planar N₄ coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol mol­ecules in the other (also as Cu—O). Inter­actions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive inter­molecular hydrogen‐bonding network.     

Two salts of 5‐sulfosalicylic acid and 3‐aminopyridine

5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C₅H₇N₂⁺·C₇H₅O₆S⁻·H₂O or 3‐APy·5‐SSA·H₂O, (I), and the anhydrous adduct, C₅H₇N₂⁺·C₇H₅O₆S⁻ or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively.     

含吡唑啉酮三脚架结构的化合物及其稀土配合物的合成、表征及荧光性能

合成了一种含吡唑啉酮的三脚架结构化合物 1,1,1 三 { 1′ [2′ 氧杂 5′ 氧代 5′ ( 1″ 苯基 3″ 甲基吡唑啉酮 4″ 基 )戊基 ] }丙烷 (H3 L)及其 7个稀土配合物。通过元素分析、摩尔电导、质谱、红外光谱、核磁共振谱、荧光光谱等对H3 L及其稀土配合物的组成及性质进行了表征。分析结果表明 :H3 L的分子式为C45H50 N6O9,配合物的组成比为REL·0 5H2 O (RE =La ,Sm ,Eu ,Gd ,Tb ,Dy ,Yb) ;该三脚架形配体分别以醚氧、烯醇氧及吡唑酮环上的羰基氧与稀土离子进行配位 ,形成内配型配合物。荧光光谱分析表明SmL·0 5H2 O ,EuL·0 5H2 O ,TbL·0 5H2 O ,DyL·0 5H2 O配合物具有三价稀土离子的特征线状荧光 ,其中TbL·0 5H2 O的荧光强度最强 ,表明T(配体 )→5D4(Tb)能级更为匹配 ,从而进行分子内能量有效传递 ;由EuL·0 5H2 O的荧光光谱图形推测 ,Eu3 +离子在该配合物中处于非对称中心     

铝（Ⅲ）—桑色素—含氧有机溶剂荧光体系的研究

本文系统研究了醇、酮等7种含氧有机溶剂对铝-桑色素络合物荧光反应的溶剂化效应。研究发现,上述有机溶剂对荧光体系均有增敏作用,以乙醇的效果最佳,使络合物的荧光强度增加6倍多。据此,本文建立了测定微量铝的高灵敏度荧光分析方法,线性范围为0～1.0μg/10ml,检测限为1.6×10~(-9)g/ml。用所建立的方法对化学试剂中的微量杂质铝进行了测定,结果令人满意。并对有机溶剂化效应的机理作了探讨。     

Electrochemical Synthesis and Characterization of Nickel(II) Complexes with N‐2‐Pyridyl‐sulfonamide Ligands

Heteroleptic nickel(II) complexes [NiL₂L′] of a series of monoanionic and potentially bidentate N‐2‐pyridyl‐sulfonamide ligands [HL] and 2,2′‐bipyridine or 1,10‐Phenanthroline (L′) have been prepared by electrochemical oxidation of a nickel anode in an acetonitrile solution of the ligands. The complexes have been characterized by microanalysis, IR and electronic spectroscopy, magnetic measurements and LSI mass spectrometry. The crystal structure of [Ni(Ms6mepy)₂(bipy)] has been determined by x‐ray diffraction and shows the metal in an octahedral NiN₆ environment. Octahedral structures are also proposed for the other complexes with the N‐2‐pyridyl‐sulfonamide ligands acting as N,N′ or N, O bidentate systems, depending on the position of the methyl substituent on the pyridine ring.     

Two‐Dimensional Holo‐ and Hemidirected Lead(II) Coordination Polymers: Synthetic,Spectroscopic, Thermal,and Structural Studies of [Pb(μ‐SCN)2(μ‐ebp)1.5]n and {[Pb(μ‐OAc)(μ‐ebp)](ClO4)}n (ebp=4,4′‐[(1E)‐Ethane‐1,2‐diyl]bis[pyridine]; OAc=Acetato)

Two new coordination polymers of Pb^II complexes with bridging 4,4′‐[(1E)‐ethane‐1,2‐diyl]bis[pyridine] (ebp), thiocyanato, and acetato ligands, [Pb(μ‐SCN)₂(μ‐ebp)_1.5]_n ( 1 ) and {[Pb(μ‐OAc)(μ‐ebp)](ClO₄)}_n ( 2 ), were synthesized and characterized by elemental analysis, FT‐IR, ¹H‐ and ¹³C‐NMR, thermal analysis, and single‐crystal X‐ray diffraction. In 1 , the Pb²⁺ ions are doubly bridged by both the ebp and the SCN⁻ ligands into a two‐dimensional polymeric network. The seven‐coordinate geometry around the Pb²⁺ ion in 1 is a distorted monocapped trigonal prism, in which the Pb²⁺ ions have a less‐common holodirected geometry. In 2 , the Pb²⁺ ions are bridged by AcO⁻ ligands forming linear chains, which are also further bridged by the neutral ebp ligands into a two‐dimensional polymeric framework. The Pb²⁺ ions have a five‐coordinate geometry with two N‐atoms from two ebp ligands and three O‐atoms of AcO⁻. Although ClO acts as a counter‐ion, it also makes weak interactions with the Pb²⁺ center. The arrangement of the ligands in 2 exhibits hemidirected geometry, and the coordination gap around the Pb²⁺ ion is possibly occupied by a configurationally active lone pair of electrons.     

New ent‐Abietanoids from Isodon rubescens

Six new ent‐abietane diterpenoids, rubescensins I–M ( 1 – 5 ) and P ( 6 ), along with two related acetonide derivatives ( 7 and 8 ), were isolated from Isodon rubescens. Their structures were elucidated by detailed spectroscopic analysis. Compound 5 is the first N‐containing diterpenoid from the genus Isodon, exhibiting notable cytotoxicity against human tumor K562 cells.     

Utility of N‐[4‐(N‐Substituted Sulfamoyl)Phenyl] Cyanothioformamides in the Synthesis of Heterocyclic Compounds

The novel cyanothioformamides 2a‐d were prepared by treatment of isothiocyanatosulfonamides 1a‐d with potassium cyanide at room temperature. Cyclocondensation of compounds 2b,c with phenyl isocyanate as electrophile furnished the corresponding imidazolidines 3a,b . The reactivity of compound 3a towards some nitrogen nucleophiles was investigated. Thus, the thiosemicarbazone 4 and imidazo[4,5‐b]quinoxaline 6 were synthesized by condensation of compound 3a with thiosemicarbazide and o‐phenylenediamine, respectively. Treatment of 3a with hydrochloric acid afforded compound 7 . Our investigation was extended to include the reactivity of cyanothioformamide 2 towards o‐aminophenol, anthranilic acid, and o‐phenylenediamine and yielded the corresponding heterocycles 9 , 11 and 13 derivatives, respectively. Structures of the synthesized compounds were established by their elemental analysis and spectral data.     

邻苯二甲酸在异丙醇-水混合溶剂中电离热力学性质的研究

The first thermodynamic dissociation constants of o-phthalic acid were determined at five temperatures from 278.15 to 318.15 K in 10, 14.93 and 20 wt% isopropanol-water solvent mixtures, by precise e. m. f. measurements of hydrogen-silver chlorld electrodes in cells without liquid junction. On the basis of Pitzer's theory, the method of polynomial approximation was used to determine the dissociation constants of H_2P and the results obtained were compared with traditional extrapolation according to the extended Debye-Huckel equation Results obtained from both methods agree within experimental error. The dependence of the first thermodynamic dissociation constant on temperature was given as a function of the thermodynamic temperature T by the empirical equation: pK_1=A_0+A_1/T+A_2/T. The thermodynamic quantities of dissociation in the mixed solvents have been calculated, and the results have been discussed.     

MnOx在ZrO2上分散状态及对CO氧化的影响

近年，氧化铝载体以其独特性能引起多方面的关注［1］．当将Pt、Rh金属担载在ZrO2上时，在金属和氧化物之间存在着强的相互作用［2，3］，从而提高了CO氧化和NO的还原性能．目前，许多作者曾对ZrO2。负载氧化铜催化剂进行了较系统的研究[4，5]：氧化锰对许多重要的催化反应有广