Design of a capillary-microreactor for efficient Suzuki coupling reactions

A Pyrex glass capillary (0.4 mm internal diameter) microreactor was developed and used for Suzuki coupling reactions. Capillary-microreactors are more attractive than photolithographic microfluidic devices in terms of simplicity, low cost and ease of handling. Compared with the conventional synthesis procedure, our approach of using a capillary-microreactor offers a convenient and highly efficient means to optimize reaction conditions and the performance of catalysts. The procedure exhibits good precision, reproducibility and high reaction yield for a range of reactants investigated.     

基于聚类分析的初三化学学业质量发展研究

以2013-2016年广州市各区（县级市）中考化学成绩的4种数据为指标，运用聚类分析研究广州市区域初三化学学业质量的发展状况。研究发现各区（县级市）主要分为3大类，部分区在不同年份的类别中移动，倾向于建立一个包括越来越多区域的第1大类。广州市区域初三化学学业质量逐步向优质均衡发展。系统的中学生化学探究活动和化学教师研训活动是实现这一发展的重要原因。     

Molecular recognition of l-leucyl-l-alanine: enantioselective inclusion of alkyl methyl sulfoxides

A simple aliphatic dipeptide, l-leucyl-l-alanine (Leu-Ala), includes several alkyl methyl sulfoxides enantioselectively to form inclusion crystals. From single-crystal X-ray analyses of three inclusion compounds of dimethyl sulfoxide (DMSO), isobutyl methyl sulfoxide, and benzyl methyl sulfoxide, it was elucidated that Leu-Ala molecules self-assemble to form layer structures and the sulfoxides are included via hydrogen bonding in a cavity between these layers. The inclusion cavity has methyl group and isobutyl group at its each side, and the guest sulfoxide is placed in such a manner that its methyl group faces toward the methyl of the Leu-Ala cavity. When the alkyl group of the sulfoxide is comparably large, it is located in the residual space of the cavity to attain effective crystal packing. Thus, the sulfoxides having a comparably large group such as isobutyl, butyl, and benzyl are included with a high (R)-enantioselectivity in Leu-Ala crystals.     

配合物型非线性光学材料的晶体工程

以分子基材料为目标的功能配合物的设计合成是近年来材料化学研究的重要领域，传统的分子设计尽管在分子水平上获得了很大的成功，但在由分子到晶体，由微观性质到宏观功能的晶体工程研究中遇到了极大的困难。因为宏观功能不仅要求分子本身具有良好的性能，同时还要求分子按照一定的方式堆积和排列犤１～３犦。例如二阶非线性光学材料不但要求分子具备较大的非线性超极化率和非对称中心，而且还要求分子在堆积过程中形成无心空间群的晶体。而自然界中大约超过７０％的手性分子在结晶时都形成有心的空间群，因此，如何实现分子的无心堆积是非…     

Triple hydrogen bonds direct crystal engineering of metal-assembled complexes: the effect of a novel organic-inorganic module on supramolecular structure

Novel triply hydrogen bonded suprastructures based on [M(tdpd)2(L)2]2- (H2tdpd=1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, L=solvent) and melamine-analogous cations have been synthesized and characterized. The use of anions containing two AAA sets from [M(tdpd)2(L)2]2- together with cations containing one DDD set (A=hydrogen-bond acceptor, D=hydrogen-bond donor) leads to the formation of complementary triply hydrogen bonded modules in the solid state. In all cases, the building module is further extended via additional hydrogen-bonding interactions to produce a tape, and tapes are assembled into sheets. These results show that a hydrogen-bonded module consisting of different kinds of building blocks, one of which is a metal complex that includes hydrogen-bond acceptor sites and the other is a hydrogen-bond donor molecule, will be attractive for constructing metal-containing supramolecular systems by the self-assembly technique.     

Preparation and Crystal Structures of 4-(4′-Pyridylthio)-1-methylpyridinium Salts: Assembly of a Donor-Acceptor-Type Molecule Containing a Sulfide Bridge

A series of ionic 4-(4′-pyridylthio)-1-methylpyridinium salts with different counteranions (1, I⁻; 2, BF⁻₄; 3, PF⁻₆; and 4, OTf⁻, where OTf=trifluoromethanesulfonate) have been prepared. Structural analysis reveals that the cation exhibits a variety of stacking structures dependent on the anion. Compound 1 crystallizes in space group P2_1/n (#14), with a=10.764(3) Å, b=9.601(5) Å, c=13.105(3) Å, β=108.35(2), V=1285.4(8) ų, and Z=4. In this compound, each cation moiety is stacked in a helical arrangement along the c-axis. Compound 2, which is isomorphous to 1, has space group P2_1/n (#14), with a=11.647(2) Å, b=9.203(3) Å, c=13.232(2) Å, β=108.42(2), V=1345.6(5) ų, and Z=4. Compound 3 crystallizes in space group P2_1/n (#14), with a=8.06(1) Å, b=17.43(1) Å, c=10.30(1) Å, β=103.0(1), V=1410(3) ų, and Z=4. In this salt, the cation molecules assume a head-to-tail stacking arrangement, forming a polar pseudo 1-D chain. Compound 4 crystallizes in space group Pb? (#2), with a=7.585(4) Å, b=15.443(7) Å, c=6.775(4) Å, α=99.33(4), β=108.35(2)^o, γ=98.37(4), V=756.6(7) ų, and Z=2. The structure of 4 consists of a columnar stacking of pyridine moieties, with the cation moieties surrounded by the counteranions. Calculations show that the 4-(4′-pyridylthio)-1-methylpyridinium cation may be a good building block for second harmonic generation (SHG) materials, even though salts 1-4 crystallized in centrosymmetric structures and were SHG inactive.     

Crystal engineering: Supramolecular structures by cocrystallization ofMeso-1,2-diphenyl-1,2-ethanediol and bisimines,simple cases of molecular recognition

The crystal structures of molecular complexes betweenmeso- 1,2-diphenyl-1,2-ethanediol and two bisimines (N,N-(dibenzylidene)-ethylenediamine and glyoxylidene-bis(2,4-dimethyl-3-pentyl-amine) are reported at different temperatures. The structure-determining motif of the cocrystalline arrangement is one single O-H . N hydrogen bond resulting in infinite ladderlike polymers. The supramolecular structure is formed by recognition of fitting species: Thed- orl-isomers do not arrange in such structures.¹H NMR experiments show that no prearrangements take place by forming complexes in solution.     

从能源产业发展和人才需求浅谈“能源化学”新工科改造

Based on building emerging engineering education of "energy chemistry", we investigated the state key petro-chemical enterprises according to the industrial development and the demand of professional talents. The research report summarizes, analyzes and discusses the current priority development fields of industry, the talent training status, curriculum structure and education program of the chemistry and chemical engineering in universities. The ideas on emerging engineering education of "energy chemistry" have been proposed, and it will be beneficial to building a novel education program for talents training, which integrates the principle of chemistry, energy conversion and information science, etc.     

Correlation between Solution and the Solid State: The pH Dependent Composition in the Ternary System [Co(H2O)6]2+ or [Ni(H2O)6]2+/Piperazine/Phosphate

The protolytic equilibria of piperazine (C₄H₁₀N₂) and phosphate have been investigated in the presence of cobalt or nickel chloride or nitrate by potentiometric titrations between pH 2 and 8. Potentiometric titrations suggest the presence of [M²⁺(H₂O)₅(C₄H₁₁N₂⁺)]³⁺ and [M²⁺(H₂O)₅(C₄H₁₀N₂)]²⁺ in solution with stability constants logK of 3.1 and 3.8 for M = Co and 3.1 and 3.6 for M = Ni, respectively. Crystallization experiments were then conducted at selected pH values to isolate desired species from the known solution composition. Crystallization afforded [M(H₂O)₆]²⁺(C₄H₁₂N₂²⁺)(HPO₄^2—)₂ at pH 3.5 and 6.2 (M = Co, Ni), and Co₃(PO₄)₂·8H₂O at pH 10.5. No crystals with the dihydrogenphosphate anion or a metal‐bound piperazine ligand could be isolated under the reaction conditions. The solid‐state assembly in the isomorphous structures of [M(H₂O)₆](C₄H₁₂N₂)(HPO₄)₂ with M = Co and Ni is based on an extended hydrogen bonded network between the three ionic building blocks.