Convenient synthesis of Pt(0) olefin complexes by colorimetric reduction of Pt(II) complexes with SmI2

Homoleptic olefin platinum(0) complexes, Pt(C₇H₁₀)₃ and Pt(cod)₂, were synthesized by the colorimetric reduction of platinum(II) complexes with SmI₂ in the presence of 2-norbornene or COD. This is a practically more convenient method for the synthesis of the Pt(0) complexes than the literature method employing Li₂(cot).     

Pre-regulation of the planar chirality of pillar[5]arenes for preparing discrete chiral nanotubes

Regulating the chirality of macrocyclic host molecules and supramolecular assemblies is crucial because chirality often plays a role in governing the properties of these systems. Herein, we describe pillar[5]arene-based chiral nanotube formation via pre-regulation of the building blocks'' chirality, which is different from frequently used post-regulation strategies. The planar chirality of rim-differentiated pillar[5]arenes is initially regulated by chiral awakening and further induction/inversion through stepwise achiral external stimuli. The pre-regulated chiral information is well stored in discrete nanotubes by interacting with a per-alkylamino-substituted pillar[5]arene. Such pre-regulation is more efficient than post-regulating the chirality of nanotubes.

Pillar[5]arene-based chiral nanotube formation via pre-regulation of the building blocks'' chirality is more efficient than post-regulating the chirality of nanotubes.     

Effect of drying on the mesoporous structure of sol-gel derived silica with PPO-PEO-PPO template block copolymer

The effects of drying method on the pore structure of mesoporous silica were studied from the viewpoint of enhancing closed porosity in mesoporous silica. The mesoporous silica was prepared via a sol-gel process using polyethyleneoxide-polypropyleneoxide-polyethyleneoxide (PEO-PPO-PEO) triblock copolymer (Pluronic P123) as the structure-directing template. The closed porosity was evaluated from the apparent mass density of the sample measured by a helium pycnometer. These mesoporous silicas were also characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and nitrogen adsorption. The drying method was shown to be responsible for the finally templated mesoporous structure of the silica. More rapid drying is more preferable for enhancing the closed porosity of the mesoporous silica. The closed pores were formed by immediate immobilization of copolymer molecular assemblies in the silica matrix due to the instant removal of the solvent and solidification at higher temperatures. The drying method, mainly affecting the drying rate, is highly influential on the finally replicated mesoporous structure in silica.     

Copper‐Catalyzed Reaction of Trifluoromethylketones with Aldehydes via a Copper Difluoroenolate

A copper‐catalyzed reaction of easily accessible α,α,α‐trifluoromethylketones with various aldehydes affords difluoro‐methylene compounds in the presence of diboron and NaOtBu. The key process of the reaction is the formation of a copper difluoroenolate by 1,2‐addition of a borylcopper intermediate to α,α,α‐trifluoromethylketones and subsequent β‐fluoride elimination. Mechanistic studies including the isolation and characterization of a possible anionic copper alkoxide intermediate are also described.     

Reductive coupling of metal triangles in sandwich complexes

The one-electron reduction of [Pd3(C7H7)2(CH3CN)3][BF4]2 in acetonitrile resulted in the formation of the dimer dication [Pd6(C7H7)4(CH3CN)4][BF4]2, whose structure containing a novel bitriangle hexapalladium skeleton was determined by X-ray crystallographic analysis. The dimer is stable in CD3CN at ambient temperature for several days but is highly air-sensitive. Similarly, the cycloheptatriene tripalladium complex [Pd3(C7H7R)2(CH3CN)3][BF4]2 (R = H, t-Bu) dimerized upon one-electron reduction. Both monomer and dimer of cycloheptatriene complexes were structurally determined by X-ray crystallographic analyses.     

Intramolecular arylcyanation of alkenes catalyzed by nickel/AlMe2Cl

A catalyst system derived from nickel and cocatalytic AlMe2Cl effects the intramolecular arylcyanation of alkenes. The reaction takes place in an exclusive exo-dig manner to give a wide range of nitriles having a benzylic quaternary carbon in good yields. Detailed investigations are described on the scope and mechanism as well as preliminary results on the asymmetric version of the reaction to provide novel access to chiral quaternary stereocenters.     

稀土掺杂PVC的紫外及微波交联研究

聚氯乙烯 (ＰＶＣ)是我国目前产量最大 ,应用面最广的高分子原材料。但其耐热性、稳定性及抗老化性都较差。我们考虑到使用稀土掺杂以改进其相关性能 ,同时掺入了少量从水玻璃中提取出来的活性硅醇到ＰＶＣ中以增加其柔性 ,探索了紫外辐射交联和微波辐射交联对ＰＶＣ机械力学性能的影响。本文采用ＰＶＣ流延膜来进行辐射交联并测定样品的力学性能。结果发现 ,稀土掺杂的结果使得样品的扯断伸长率大幅度提高 ,拉伸强度上升显著。而添加活性硅醇后ＰＶＣ流延膜的扯断伸长率进一步提高 ,拉伸强度则下降 ,柔性得以提高。将氯化钕溶于 95 %的乙醇…     

In-plane mechanical behaviors of 2D repetitive frameworks with four-coordinate flexible joints and elbowed beam members

The mechanical properties of an open-framework structure constructed of joints and beam members are strongly influenced by both its geometrical configuration and joint flexibility. This paper clarifies the relationship between joint flexibility and Poisson's ratio, which is a mechanical criterion for solid deformation, and discusses two types of in-plane anisotropic structures made up of four-coordinate flexible joints and elbowed beam members. Uniaxial tensile analyses estimate the linear and nonlinear elastic properties of these frameworks by applying straightforward joint modeling with multi-rotational degrees of freedom. The numerical results show that these proposed frameworks produce a variety of deformability dependent on the joint flexibility in auxetic deformation with a negative Poisson's ratio, the folding mechanics under kinematic indeterminacy, and the transition of Poisson's ratio between the positive and negative values. The geometrical and topological aspects of the obtained mechanical behaviors are discussed.