Metal complexes derived from hydrazoneoxime ligands: II. Synthesis,electrospray mass spectra and magnetochemical studies of some copper(II) complexes derived from p-substituted aroylhydrazoneoximes

Mono- and binuclear copper(II) complexes derived from substituted aroylhydrazoneoximes of the general formulae [Cu(H₂LR)Cl₂]·nH₂O, [Cu(HLR)Cl], [{Cu(HLR)}₂]·2NO₃·nH₂O and [{Cu(LR)}₂]·nH₂O have been prepared and characterized, where H₂LR, HLR and LR refer, respectively, to the neutral, monoanionic and dianionic ONN tridentate aroylhydrazoneoxime ligands. Electrospray ionization (ESI) mass spectra revealed the formation of tri- and tetranuclear copper(II) complexes in dimethylformamide (DMF) or dimethysulphoxide (DMSO) solutions. The effect of substitution in the aroylhydrazone residue on the degree of deprotonation of the ligand and the energies of d–d transitions of the copper(II) complexes have been studied. Tuning of the antiferromagnetic exchange coupling by different substituents in [{Cu(HLR)}₂]·2NO₃·nH₂O and [{Cu(LR)}₂]·nH₂O complexes have been discussed.     

Syntheses and crystal structures of two cadmium coordination polymers [Cd(2-mBIM)(NCS)(SCN)] n and [Cd2(2-mBIM)2(NO3)2(C4H4O4)(H2O)5] n based on bis(2-methylimidazol-1-yl)methane

Two cadmium(II) coordination polymers, [Cd(2-mBIM)(NCS)(SCN)] _n (1) and [Cd₂(2-mBIM)₂(NO₃)₂(C₄H₄O₄)(H₂O)₅] _n (2) (2-mBIM = bis(2-methylimidazo-1-yl)methane, C₄H₄O₄= succinate), have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 with a = 9.0770(5) Å, b = 9.4043(4) Å, c = 19.8720(9) Å, α = 101.551(1)°, β = 93.498(1)°, γ = 108.484(1)°, V = 1562.02(13) ų, and Z = 2. Each Cd(II) is octahedrally coordinated and connected with two adjacent Cd(II)'s by double end-to-end thiocyanate bridges, resulting in the formation of 1-D zigzag chains, linked to each other via bridging 2-mBIM giving a 2-D supramolecular framework. Complex 2 crystallizes in the monoclinic space group P2(1)/n with a = 12.6543(6) Å, b = 7.7128(4) Å, c = 17.3089(9) Å, β = 109.3980(10)°, V = 1593.45(14) ų, and Z = 2. Cd(II) is coordinated with oxygen and nitrogens from two independent 2-mBIM, in a cis-configuration to form a 1-D helical structure. A 3-D supramolecular network comprised of succinate anion bridged 1-D helical chains, and weak hydrogen bonds between dimer waters gave 2-D layers.     

氢键桥联双核铜配合物磁耦合的密度泛函研究

在密度泛函理论的基础上,应用对称性破损方法研究了氢键桥联双核铜模型配合物的磁耦合行为以及磁耦合常数随O-O距离的变化趋势.计算结果表明,反铁磁耦合作用来源于Cu原子的d_x²-y²和氧原子的p_x或p_y磁轨道的部分重叠,而H原子不参与磁耦合作用.磁耦合常数J与O-O距离r之间存在指数关系,而不是线性关系.     

一种空间缆索结构静力分析的解析元法

将空间缆索结构简化为具有拉伸刚度的质点系,给出了缆索结构空间解析元法的基本方程和求解方法,单元间的作用力与坐标变化的关系可以用解析法得到,对所得到的反映结构特性的质点系方程组进行力的平衡迭代,求解方程组.采用自动的动态可变步长的迭代方法,能够提高计算效率,保证收敛.这种方法既考虑了几何非线性,又适用于材料非线性的计算,比有限元法优越之处还在于,它不用求解线性方程组,所以适用范围广,允许求解多自由度的几何可变体系,而有限元法在求解此类问题时经常不收敛.     

Molecular Bridges Stabilize Graphene Oxide Membranes in Water

Recent innovations highlight the great potential of two‐dimensional graphene oxide (GO) films in water‐related applications. However, undesirable water‐induced effects, such as the redispersion and peeling of stacked GO laminates, greatly limit their performance and impact their practical application. It remains a great challenge to stabilize GO membranes in water. A molecular bridge strategy is reported in which an interlaminar short‐chain molecular bridge generates a robust GO laminate that resists the tendency to swell. Furthermore, an interfacial long‐chain molecular bridge adheres the GO laminate to a porous substrate to increase the mechanical strength of the membrane. By rationally creating and tuning the molecular bridges, the stabilized GO membranes can exhibit outstanding durability in harsh operating conditions, such as cross‐flow, high‐pressure, and long‐term filtration. This general and scalable stabilizing approach for GO membranes provides new opportunities for reliable two‐dimensional laminar films used in aqueous environments.     

Nonlinear models of suspension bridges

Nonlinear variational equations describing one type of suspension bridges are proposed and studied. The variational equations describe the behaviour of road bed, main cables and cable stays. The road bed is described by two functions connected with vertical and horizontal deformation of any cross section. The main cable is considered to be perfectly flexible and inextensible. The cable stays only resist tensile forces. The variational equations are derived from the principle of minimum potential energy. The existence of solution is based on the Brouwer Fixed Point Theorem. The local uniqueness and continuous dependence on the data represented by gravitational forces acting on the road bed are studied. The local results are based on the Implicit Function Theorem for Banach spaces. A certain stability criterion for suspension bridges is formulated and this criterion indicates how to influence the stability of suspension bridges.     

Synthesen und Kristallstrukturen der chalkogenidoverbrückten Nickelclusterverbindungen [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6] und [Ni18S18(PiPr3)6]

Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni₅Se₄Cl₂(PPhEt₂)₆], [Ni₁₂Se₁₂(PⁿPr₃)₆], and [Ni₁₈S₁₈(PⁱPr₃)₆] The reaction of (R)ESiMe₃ (R = SiMe₃, Mes = C₉H₁₁; E = S, Se) with [NiCl₂(PPhEt₂)₂] and [NiCl₂(PR₃)₂] (R = ⁿPr, ⁱPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni₅Se₄Cl₂(PPhEt₂)₆]·2THF ( 1 ), [Ni₁₂Se₁₂(PⁿPr₃)₆]·2THF ( 2 ), and [Ni₁₈S₁₈(PⁱPr₃)₆]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses.     

Monte Carlo study of three-dimensional organization of water molecules around DNA fragments

Interactions with water molecules are important for the stabilization of three-dimensional structures of nucleic acids and for their functioning. The first hydration shells of macromolecules can be considered as structural parts of nucleic acid. We performed a Monte Carlo study of systems containing a nucleic acid base or base pair with water molecules using improved potential functions. These potential functions enable experimental data on both single base–single water interaction energies and enthalpies of base hydration to be reproduced. Hydration shell structures of base pairs are dependent on the pair geometry. Structural elements of hydration shells can contribute to the pair stability and hence to the probability of mispair formation during nucleic acid biosynthesis. The distribution of water molecules around bases and base pairs is essentially nonhomogeneous.From the Proceedings of the 28th Congreso de Químicos Teóricos de Expresión Latina (QUITEL 2002).