Halogen bonds and metal bonds involving superalkalies M2OCN/M2NCO (M = Li,Na) complexes

Structural Chemistry - A new type of halogen bond formed by supermetals or superalkalies with dihalogen molecules was analyzed by means of ab initio at the MP2/aug-cc-pVTZ level. The results reveal...     

High and selective CO2 capture by two mesoporous acylamide-functionalized rht-type metal-organic frameworks

Two mesoporous and flexible acylamide-functionalized rht-type MOFs exhibit not only high excess unsaturation CO(2) uptake (157 wt%) at 20 bar and 273 K, but also good selectivity of CO(2)/CH(4) (8.6) and CO(2)/N(2) (34.3). The advantages of acylamide groups for CO(2) capture have been further confirmed by GCMC and first-principles calculations.     

冲击荷载下C型G550冷弯钢的断裂机理研究

以C型G550薄壁冷弯钢构件为研究对象, 通过材料在不同应变率下的拉伸实验和数值模拟数据得到Johnson-Cook (J-C)本构模型和Johnson-Cook失效模型参数. 通过Abaqus软件模拟了不同冲击荷载作用下C型冷弯钢构件撕裂破坏的全过程, 利用落锤装置轴向冲击试验进行对比, 其实验结果与有限元数值模拟结果有良好的一致性. 此外, 对冲击试样撕裂断口进行微观形貌分析, 得到构件的断裂机理. 结果表明: 随着冲击速度的提高, 冲击力对构件的加载时间增加, 构件需要较大的塑性变形来吸收冲击能量; 冲击速度越高, 裂纹扩展功所占吸收冲击能量的比例越大, 显示出高速下裂纹扩展的能力越好; 冲击速度较高时, 以脆性断裂为主, 断口出现解理面, 甚至在高速变形时发生了绝热剪切破坏.     

NMR and theoretical study on interactions between diperoxovanadate complex and pyrazole-like ligands

To understand the effects of pyrazole substitution on reaction equilibrium, the interactions between a series of pyrazole-like ligands and [OV(O₂)₂(D₂O)]^?/[OV(O₂)₂(HOD)]^? were explored by using multinuclear (¹H, ¹³C, and ⁵¹V) magnetic resonance, HSQC, and variable temperature NMR in 0.15 mol/L NaCl ionic medium mimicking physiological conditions. These results show that the relative reactivities among the pyrazole-like ligands are 3-methyl-1H-pyrazole ≈ 4-methyl-1H-pyrazole ≈ 1H-pyrazole > 1-methyl-1H-pyrazole. As a result, the main factor which affects the reaction equilibrium is the steric effect instead of the electronic effect of the methyl group of these ligands. A pair of isomers has been formed resulting from the coordination of 3-methyl-1H-pyrazole and a vanadium complex, which is attributed to different types of coordination between the vanadium atom and the ligands. Thus, the competitive coordination leads to the formation of a series of six-coordinate peroxovanadate species [OV(O₂)₂L]^? (L, pyrazole-like ligands). Moreover, the results of density functional calculations provided a reasonable explanation on the relative reactivity of the pyrazole-like ligands as well as the important role of solvation in these reactions.     

Enhanced CO2 binding affinity of a high-uptake rht-type metal-organic framework decorated with acylamide groups

An rht-type metal-organic framework (MOF) prepared from M(2)(carboxylate)(4) (M = Cu, Co) paddlewheel clusters and a flexible C(3)-symmetric hexacarboxylate ligand with acylamide groups exhibits larger CO(2) uptake, an enhanced heat of adsorption, and higher selectivity toward CO(2)/N(2) in comparison with what was previously observed for an analogous MOF with alkyne groups.     

横向约束槽钢截面柱畸变屈曲分析

提出了用于计算冷弯薄壁槽钢柱畸变屈曲临界应力的加劲板模型。在加劲板模型中,腹板视为板单元,而翼缘和卷边则假设为在腹板两端施加的角加劲肋,因此槽钢截面构件可视为腹板(板)与翼缘-卷边(角加劲)组成的加劲板。通过加劲板模型,可以考虑腹板与翼缘-卷边之间相互约束效应,并基于最小势能原理,推导出构件畸变屈曲临界应力计算公式。为了验证加劲板模型的正确性,以槽钢柱为例,对选用的构件进行畸变屈曲临界应力计算,并与有限条程序计算结果进行比较,平均误差为4.0%,从而验证了本文模型的正确性。     

Z型Q345冷弯钢构件率相关本构模型下的动态冲击失稳研究

以Z型Q345薄壁冷弯钢构件为研究对象, 首先测试了试验钢在10-4~102s-1应变率内的材料力学属性, 并拟合得到了由Johnson-Cook本构模型表述的材料本构参数, 同时对拉伸断裂的试件断口做了微观形貌分析. 接着, 在落锤装置上对Z型冷弯钢构件做不同速度的轴向冲击试验, 研究构件受到冲击的动态失稳变形情况. 然后, 通过ABAQUS软件建立了可以反映锤头冲击构件过程的仿真模型, 考虑应变率效应和初始缺陷等因素, 分析了构件主要部位端部质点的位移和速度变化情况以及应力波传播效应的影响. 结果表明 薄壁冷弯钢构件受到外部冲击作用会产生动态屈曲, 随着冲击载荷增大, 发展为明显的塑性变形. 应力波的传播效应对动态屈曲模态的阶跃起着关键的作用.     

Controlling the shifting degree of interpenetrated metal-organic frameworks by modulator and temperature and their hydrogen adsorption properties

For the first time, the shifting degree of pcu-type interpenetrated framework was well controlled by employing a modulator and changing the temperature, in which their evacuated samples are almost non-crystalline products with different meso- and microstructures, resulting in different hydrogen adsorption properties.     

Highly selective CO2 capture of an agw-type metal-organic framework with inserted amides: experimental and theoretical studies

An amide-inserted metal-organic framework (NJU-Bai3) presents high storage and high selectivity toward CO(2) and combines these two interesting characters which strongly support our expectation that amide groups can significantly enhance the CO(2) binding ability and selectivity of MOFs.     

Regium bonds formed by MX (M═Cu,Ag, Au; X═F,Cl, Br) with phosphine-oxide/phosphinous acid: comparisons between oxygen-shared and phosphine-shared complexes

ABSTRACT

Regium bonds interaction between phosphine oxide (H₃PO), the trans phosphinuous acid (T-PH₂OH), the cis phosphinuous acid (C-PH₂OH) and MX (M═Cu, Ag, Au; X═F, Cl, Br) complexes were investigated by means of ab initio MP2/aug-cc-pVTZ method. For phosphinuous acid and MX complexes, two types of regium bonded interaction (trans and cis complexes) are observed and the two types of structures are very easily transformed from one type to another due to a low energy barrier. The molecular interaction energies are in the order of Au?>?Cu?>?Ag, F?>?Cl?>?Br and increase with the decrease of intermolecular distance R_int. Two resonance-type structures of P:M-X (ωI) ? P–M:X (ωII), O:M-X (ωI) ? O–M:X (ωII) are recognised by the natural resonance theory (NRT) and the natural bond orbitals (NBOs) analysis. The competition between ωI ? ωII resonance structures mainly arises from hyperconjugation interactions, in all phosphor-shared complexes, P–M:X resonance accounts for a larger proportion which leads to the covalent characters. All of complexes have been described in terms of their electron density properties.