锌(Ⅱ)与2,2′-联吡啶胺(dpa)和3-苯丙酸(HPPr)混配配合物的合成、晶体结构及性质表征

合成了锌（Ⅱ）与２，２′－联吡啶胺（ｄｐａ）和３－苯丙酸（ＨＰＰｒ）混配配合物［Ｚｎ（ｄｐａ）（ＰＰｒ）２］·２Ｈ２Ｏ，并测定其晶体结构．晶体属三斜晶系，Ｐ１空间群，晶胞参数ａ＝１０．５４１（１）ｎｍ，ｂ＝１１．３３３（１）ｎｍ，ｃ＝１１．６９８（１）ｎｍ，α＝９１．００（１）°，β＝９０．９６（１）°，γ＝８８．３８（１）°，Ｚ＝２，２个ＰＰｒ－１羧基上的４个氧原子、１个ｄｐａ上的２个氮原子分别与中心离子Ｚｎ（Ⅱ）配位，构型为畸变八面体．２个结晶水与配体间可能存在着分子内氢键．通过元素分析、ＩＲ、摩尔电导和热重分析表征了配合物的结构．     

Synthesis,structure, and magnetic properties of the cobalt(<Emphasis Type="SmallCaps">II</Emphasis>) 1,3,5-benzenetricarboxylate layered coordination polymer

The reaction of Co(NO₃)₂·6H₂O with 1,3,5-benzenetricarboxylic acid (H₃btc, trimesic acid) in DMF at 100 °C afforded the coordination polymer [Co₃(dmf)₆(btc)(Hbtc)(H₂btc)]··9H₂O (1) (dmf is N,N′-dimethylformamide, DMF). According to the X-ray diffraction study, the metal-organic coordination polymer is composed of planar honeycomb (6,3) networks, in which the organic benzenetricarboxylate anions and the inorganic Co²⁺ cations play a role of three-connected nodes. Disordered water molecules are intercalated between the layers. A study of the magnetic properties showed the presence of a weak antiferromagnetic coupling between the Co²⁺ ions (S = 3/2). Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1719–1723, September, 2007.     

有机金属络合物用于高分子富氧膜的研究进展

本文介绍了能够可逆吸附分子氧的有机金属络合物用于高分子富氧膜的研究进展，以及以双重吸附理论进行的膜的促进输送机理。     

Synthesis and Crystal Structure of a Zinc(II) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

1 INTRODUCTION The donor properties of pyridine N-oxide and its substituted derivatives to form metal complexes have been widely investigated[1～3]. The resulting comple- xes were used as drugs[4] and catalysts[5]. So far, there have been a few reports on the synthesis of Schiff base derived from picolinaldehyde N-oxide with se- micarbazone (PNOS Scheme 1) and its metal com- plexes. And crystal structures of the complexes of PNOS with Au(III)[6], Pd(II)[7] and Cu(II)[8] were re- …     

Vapor pressure,speciation, and chemical activities in highly concentrated sodium borate solutions at 277 and 317°C

The system H₂O-B₂O₃-Na₂O has been studied experimentally at 277 and 317°C. The activities of water and boric acid have been determined at mole ratios Na/B from 0 to 1.5, and total dissolved solids 3 to 80 weight percent. The activity of boric acid has been fitted to within experimental error using a speciation model with eight complex species. This model is consistent with the model previously published by Mesmer et al. The electrolyte properties of the liquid are modeled using the Pitzer-Simonson model of very concentrated electrolyte solutions. The calculated values of water activity agree with experiment, and the activity of NaOH and pOH have also been calculated. The potassium borate system also was briefly studied at 317°C, and is adequately described by a model with five complex species. The potassium borate liquid is more alkaline at K/B= 1 than a sodium borate liquid at the same mole ratio, but pOH in the two systems is the same at lower mole ratios.     

Thermodynamic Insight into the Origin of a Calix[n]arene-[60]fullerene Interaction and its Application to a Porphyrin-[60]fullerene Energy Transfer System

The calixarene-fullerene interaction,which causes only a slight change in the absorptionspectra, has been substantiated by calorimetricmeasurements: the H° values arecomparable with those obtained from the associationconstants estimated by a spectroscopic method. Furthermore, we determined the association constantbetween homooxacalix[3]arene and [60]fullerenederivatives with a porphyrin moiety by fluorescencespectra.     

一维链配位聚合物[Mn(acacen){N(CN)2}]n的合成、结构和性质的研究(英)

The manganese(Ⅲ) complex [Mn(acacen){N(CN)₂}]_n [H₂acacen=bis(acetylacetone)ethylenediimine] has been synthesized and the structure has been determined. The complex forms a one-dimensional chain structure via the bidentate bridge ligand μ_1,5-[N(CN)₂]^- linking [Mn(acacen)] moiety. The magnetic property of the compound (75～300 K) shows the existence of an antiferromagnetic exchange interaction among paramagnetic centers along the chain. CCDC: 244940.     

铈杂多配离子-水滑石超分子层柱材料ZnAl-Ce(PMoV)2的插层组装、表征及催化性能

以十四酸根阴离子柱撑Zn-Al水滑石Zn0.77Al0.22(OH)2.0.22C13H27COO.0.81 H2O(记为ZnAl-14A)为预撑前体,在水溶液中用离子交换法将以2∶17缺位杂多酸根离子(P2Mo16VO61)11-记为(P Mo V)为配体的稀土杂多配阴离子Ce(P2Mo16VO61)219-(记为Ce(PMoV)2)插层组装到水滑石层板间,合成了一种具有大的层间距(3.37 nm)的超分子插层材料Zn0.77Al0.23(OH)2.0.0105[Ce(P1.9Mo15.7V1.1O61)2].0.011C13H27COO.0.83H2O(记为ZnAl-Ce(PMoV)2)。用ICP,IR,XRD和DTA对产物的组成和结构进行了表征。结果表明,该产物中Ce(PMoV)2配阴离子沿其长轴垂直于层板的方向分布于水滑石层间;产物具有规整的层状结构和热稳定性;产物对乙酸与正丁醇的酯化反应,二甘醇的脱水-环化反应和H2O2氧化环己烷的反应有良好的催化性能,且易于回收重复使用。     

A characteristic effect of pressure on inclusion complexation of phenothiazine dyes with p-sulfonatocalix[6]arene in a room-temperature ionic liquid

The inclusion complexation of p-sulfonatocalix[6]arene (Calix-S6) with three kinds of phenothiazine dyes was studied spectrophotometrically in a mixture of a room-temperature ionic liquid [bmim]BF₄ (1-butyl-3-methylimidazolium tetrafluoroborate) and ethanol. We have determined the association constants of Calix-S6 with phenothiazine dyes under external static pressure up to 767 bar in the [bmim]BF₄-ethanol and alcohol-water mixtures. With increasing external pressure, the inclusion equilibrium in the alcohol-water mixtures was shifted to the dissociation side. Conversely, the inclusion equilibrium of methylene blue (MB) and azure A (AA) in the ionic liquid mixture was shifted to the association side. From the analysis of the pressure effects, the reaction volumes ΔV for inclusion complexation were estimated as −7 to 9 cm³ mol⁻¹ in the [bmim]BF₄-ethanol mixture and 20–32 cm³ mol⁻¹ in the alcohol-water mixtures. Based on the results, we have suggested that there is a competing complexation between the included dye and [bmim]BF₄ molecules in the ionic liquid.     

Kinetics of formation of a linear polymer-polymer network system in the presence of 3d metal chelates

For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation of the network and the linear polymer is preserved. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006.