General Synthetic Route to Monosubstituted Cycloheptadienes from Organometallic Compounds

An examination of the literature reveals that only a limited number of monosubstituted cycloheptadiene compounds have been reported. An obvious synthetic route to 5-substituted -1, 3-cycloheptadiene derivatives would be the reaction of nucleophiles with the cycloheptadienyl cation, but this pathway is generally unsuccessful due to the limited stability of the cation. On the other hand, the iron tricarbonyl complex of this cation shows remarkable stability¹ and an ability to react with nucleophiles². If the -Fe(CO)₃ group could be removed easily, a facile route to this family of organic compounds would be available. This work reports our investigation of the range of nucleophiles that can be utilized and the oxidizing agents that can remove efficiently the -Fe(CO)₃ group.     

Preface

<正>Biophysical chemistry is a relatively new branch of physical chemistry.Wikipedia-the free encyclopedia describes it with the following sentences(http://en.wikipedia.org/wiki/Biophysical_chemistry,cited on November 2,2014):"Biophysical chemistry is a physical science that uses the concepts of physics and physical chemistry for the study of     

An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties

The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO₂)₃O(OH)₂]²⁺, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations.     

Enantioselective Synthesis of a Chiral Coordination Polymer with Circularly Polarized Visible Laser

Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL‐responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL‐induced enantioselective synthesis. By irradiation with either left‐handed or right‐handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left‐handed CPL resulted in crystals with a left‐handed helical structure, and right‐handed CPL led to crystals with a right‐handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.     

Hypercoal对不同炼焦煤炭化改质作用的显微镜研究

Hypercoal(HPC)被作为一种添加剂加入到两种性质不同的炼焦煤中,以探讨其对炼焦煤炭化的改质作用。通过偏光显微镜以及扫描电镜观测炭化产物的组织结构变化。结果表明,添加剂的用量以及粒径对炼焦煤炭化改质作用的大小与原料煤的煤质有关,对焦煤改质时要求添加剂颗粒的粒径较大;而对弱黏结性煤改质时,添加剂粒径较小且添加量较多更有利于黏结和熔融作用。通过添加HPC可改善焦煤因过度膨胀造成的不均匀孔隙结构,而且孔的数量与孔径减小,孔壁增厚;添加剂在炭化过程中产生的胶质体促进了弱黏结性煤的黏结和熔融,改善了炭化产物的结构。实验还考察了原料中水分、成型压力等因素对炭化产物结构的影响。结果表明,煤中水分会在炭化产物中产生特殊的孔隙结构,而成型压力对炭化改质作用则因原料煤质不同而不同。