Synthesis, crystal structure and magnetic property of a new 1D molecular material [1-(4′-chlorobenzyl)-4-aminopyridinium](+) bis(maleonitriledithiolato)nickel(-)

A new ion-pair complex, [1-(4′-chlorobenzyl)-4-aminopyridinium](+)bis(maleonitrile-dithiolato)nickel(−),[ClbzPyNH₂][Ni(mnt)₂] (1), has been prepared and characterized. X-ray single crystal structure conforms that the Ni(mnt)₂⁻ anions and [ClbzPyNH₂]⁺ cations of 1 form completely segregated uniform stacking columns with the Ni?Ni distance 3.944 Å in the Ni(mnt)₂⁻ stacking column. The temperature dependence of the magnetic susceptibility reveals that 1 undergoes a magnetic transition, and exhibits ferromagnetic interaction in the high-temperature phase and spin gap system in the low-temperature phase.     

Ionic pair complexes with well-separated columnar stack structure based on [Pt(mnt)2]- ions showing unusual magnetic transition: syntheses, crystal structures, and magnetic properties

Three ion pair complexes, [4-R-benzylpyridinium][bis(maleodinitriledithiolato)platinum(III)] (abbreviated as [RBzPy][Pt(mnt)(2)]; R = Cl (1), Br (2), or NO(2) (3)), have been synthesized. The cations and anions stack into well-separated columns in the solid state, and the Pt(III) ions form a 1-D zigzag chain within a [Pt(mnt)(2)](-) column through Pt...S, S...S, and Pt...S...Pt interactions. The chain is uniform in 1 and 2, while it alternates in 3. Unusual magnetic phase transitions from paramagnetism to diamagnetism were observed in these three complexes at approximately 275 K for 1, approximately 269 K for 2, and approximately 184 K for 3. These phase transitions were also found in DSC measurements for 1 and 2. The overall magnetic behaviors for 1-3 indicate the presence of antiferromagnetic exchange interactions in the high-temperature phase and spin-gapped systems in the low-temperature phase. Below 50 K, 2 exhibits weak ferromagnetism. The spontaneous moments are nearly repressed by a field of 1.0 T. The crystal structure of 2 at 173 K reveals that there are two crystallographically independent [Pt(mnt)(2)](-) entries in an asymmetric unit. These two crystallographically independent [Pt(mnt)(2)](-) entries satisfy the spin-canting condition, and the EPR spectra measured at room temperature exhibit anisotropic character. Therefore, the weak ferromagnetic behavior in the low-temperature region for 2 can be attributed to the spin-canting phenomenon.     

Synthesis,structure and the e.s.r. spectrum of the mixed-valence molybdovandate Na2(NH4)4[(VIVVV8Mo)O28] · 10H2O

The mixed-valence molybdovanadate compound Na₂(NH₄)₄[V^IVV^V ₈Mo)O₂₈] · 10H₂O [Vanadata(6-)tetradeca--oxotetra-₃-oxodi-₆-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH₂OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO₆ octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.     

Synthesis of the anionic fluororeceptors based on thiourea and amide groups and recognition property for α,ω-dicarboxylate

Three new neutral receptors (1, 2 and 3) containing thiourea and amide groups were synthesized by simple steps in good yields. The binding properties for anions of 1, 2 and 3 were examined by UV-vis, fluorescence, and ¹H NMR spectroscopy. Receptors 1, 2 and 3 all had a better adipate anion selectivity by comparison with other dicarboxylate anions. The association constants of 1, 2 and 3 with adipate were higher as compared to other anions (malonate, succinate, glutarate). In particular, a distinct color change was observed from light yellow to orange-red upon addition of adipate to the solution of 1 in DMSO. The UV-vis and fluorescence data indicate that a 1:1 stoichiometry complex is formed between compound 1, 2 or 3 and dicarboxylate anions through hydrogen bonding interactions.     

Synthesis and Crystal Structure of the Binuclear Complex [Pr2(C10H8N2O4)2(C10H9N2O4)2(H2O)4]·3H2O·C6H6

The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C₁₀H₁₀N₂O₄, H₂L) was prepared in H₂O‐C₂H₅OH mixed solution, and the crystal structure of [Pr₂L₂(HL)₂(H₂O)₄]·3H₂O·C₆H₆ was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr³⁺ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ₂‐bridging mode.     

改性凹凸棒的制备及对砷离子的吸附研究

针对日益严重的砷离子污染问题，本文采用灵敏简便的原子荧光分析法，探究了凹凸棒石粘土吸附剂对砷离子的吸附性能，测定了pH、吸附时间、砷离子的初始浓度等因素对凹凸棒石粘土负载铁氧化物对砷离子吸附能力的影响，并通过SEM、EDX、FTIR对所制得的吸附剂进行了表征研究，同时进行了吸附动力学和吸附等温模型的分析。研究结果表明，改性后的凹凸棒对砷离子的吸附性能有了显著提升，在较低浓度时吸附效率可达98%，该吸附符合Langmuir等温吸附模型和准二级动力学方程。     

Novel amphiphilic fluorescent graft copolymers: synthesis,characterization, and potential as gene carriers

Amphiphilic fluorescent graft copolymer (PVP‐PyATAm) was successfully synthesized by the free radical copolymerizations of hydrophobic monomer N‐acryloyl‐thioureylene‐4‐(1‐pyrene)‐butyryl amide (PyATAm) with hydrophilic precursor polymers of vinyl‐functionalized poly (N‐vinylpyrrolidone) (Acryloyl‐PVP) in DMF. FT‐IR, ¹H NMR, TEM, gel permeation chromatography‐multi‐angle laser light scattering, UV‐vis spectroscopy, viscometric measurement, and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation showed that the copolymer PVP‐ PyATAm formed spherical micelles in an aqueous solution and the size of micelles was between 50 and 70 nm in diameter. The interaction of PVP‐PyATAm copolymer and plasmid DNA was examined by agarose gel electrophoresis and TEM. Results indicated that the copolymer–DNA complexes were self‐assembled and the size of complexes was between 90 and 120 nm in diameter. Cytotoxity studies using MTT colorimetric assays suggested good biocompatibility of PVP‐PyATAm in vitro. These results suggested the potential of this graft copolymer as gene delivery carrier. Copyright © 2007 John Wiley & Sons, Ltd.     

A Novel Uranyl Complex with Dimeric Lacunary Polyoxoanion: [(A-α-SiW<Subscript>9</Subscript>O<Subscript>33</Subscript>)<Subscript>2</Subscript>K{UO<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)}<Subscript>2</Subscript>]<Superscript>11−</Superscript>

A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na₅[(A-α-SiW₉O₃₃H₃)₂K{UO₂(H₂O)}₂], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal X-ray diffraction. In the anion, two A-α-SiW₉O₃₄¹⁰⁻ groups share two terminal oxygen atoms O_d′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement. Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the U–O bonds of the uranyl cation. Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users.     

N，N-二丁基癸酰胺萃取硝酸有机相结构研究

利用界面张力、电导、FT-IR等研究了不同硝酸浓度下萃取有机相的微结构。利用Gaussian曲线拟合处理N，N-二丁基癸酰胺(DBDEA)的羰基吸收峰，结果表明体系中存在多种以氢键结合的物种如DBDEA·HNO₃、(DBDEA)₂·HNO₃等。在较高酸度下有机相中萃取剂分子自组装成小的聚集体-反相胶团，极性核由水、硝酸和萃取剂高电荷密度的极性部分构成。     

用三组份同时分离法氨化萃取分离Gd—Tb—Dy

用普通分馏萃取工艺分离物质一次只能分离两个组份,若连续分离多种物质,则需很长工艺流程.文献[1]报导了用N_(26?)萃取分离La-Pr-Nd的三出口串级实验结果.本文报导用氨化HEH(EHP)同时萃取分离Gd-Tb-Dy的串级试验结果.