主族金属有机超分子化学进展

以有机主族金属化合物为基本单元进行的超分子自组装是近年来超分子化学的研究方向之一。本文主要对6种主族p区重金属(铟、铊、锡、铅、锑及铋)的典型有机金属超分子的自组装进行探讨和总结。     

醋酸铟化合物的合成及热稳定性研究

合成了３个新的醋酸铟化合物；Ｅｔ２ＩｎＯＡｃ，ＥｔＩｎ（ＯＡｃ）２，Ｉｎ（ＯＡｃ）３，并经元素分析，ＩＲ及ＭＳ鉴定，讨论了二乙基醋酸铟化合物受热引起的歧化反应和这些化合物的热稳定性。．     

三价铟化合物在有机合成中的应用

综述了近年来三价铟化合物促进的多种有机反应及其在有机合成中的应用,其中重点讨论了三价铟化合物促进下的碳-碳键和碳-杂原子键的形成反应.     

铟试剂在有机合成中的应用

综述了近十年来铟试剂在有机合成中的应用。重点讨论了铟试剂参与的有关碳-碳键形成的反应,如羰基化合物的烯丙基化、Reformatsky反应、成环以及三氯化铟作为Lewis酸的催化反应以及铟试剂的水相反应化学。铟试剂的这些反应,尤其是水相反应具有其它金属有机试剂在化学选择性和立体选择性方面具有独特的优势。     

铟试剂促进的水相化学反应及其在有机合成中的应用*

金属铟在空气中不会被氧化,在水中也很稳定,而且无毒,易被制成各种铟盐和有机铟试剂并参与化学反应。铟盐与其他Lewis酸相比也具有良好的水相稳定性。由于铟具有低的亲杂性,在反应过程中大多数官能团都不受影响,因而铟试剂成为有机合成中常用的导向试剂,受到了人们极大的关注。本文综述了近年来金属铟、铟盐及有机铟试剂参与的水相化学反应,介绍了铟试剂促进的一些新型反应的特点和优势及在有机合成中的应用,总结了水相中铟试剂参与化学反应的最新进展,提出了铟试剂今后研究和发展的重点和方向。     

有机镓、铟芳酰腙配合物的制备与结构表征

通过芳酰腙与三甲基镓或三甲基铟的反应,制备得到了七个有机镓或铟的镓芳酰腙配合物,在配合物中金属直接与芳酰腙的氧和烯胺氮成键,形成五元环状分子内配合物。对得到的化合物通过元素分析、红外光谱、质子核磁共振和质谱进行了结构表征。     

绿色路易斯酸三卤化铟在有机合成中的应用

三卤化铟作为温和的路易斯酸可在水、醇等绿色溶剂中实现高化学选择性、高 区域选择性和高立体选择性的化学转化。综述了三卤化铟在羟醛反应和类羟醛-曼 尼希反应、Fiedel-Crafts反应、环氧化合物的重排反应、α-氨基膦酸的合成、喹 啉环系的构建、酯交换反应、Diels-Alder反应和杂Diels-Alder反应,手性呋喃二 醇的合成、水相中的叠氮解反应和二硫缩醛的制备中的应用,同时还总结了本课题 组将三卤化铟应用于Biginelli反应和还原脱氧反应的反应结果。三卤化铟在有机 合成中潜在的优势将推动“绿色化学”的发展。     

分子内电荷转移化合物自组装功能体系

本文综述了基于电荷转移作用的具有特定组装结构的功能分子体系的合成、自组装过程和性质.易于组装且结构-性能关系清晰的分子内电荷转移化合物的分子设计可以用来开发新颖的功能体系.我们阐述了通过在π共轭体系中引入杂环或杂原子或通过使用其他芳香环扩展芳香体系的共轭长度等方法合成分子内电荷转移化合物.分子内电荷转移化合物的给体/受体以及其连接基团极大地影响有机聚集体的形貌、尺寸和其光化学性能.非中心对称的超细纤维结构的独立非线性光学响应能够在光谱上和空间上被分离和调控;分子内电荷转移化合物的另一个应用是发展基于分子内电荷转移过程效率调控的分子传感器.通过分子内电荷转移化合物的可控自组装将获得新的或改进的化学和物理性质,该方法将被广泛应用于光学、电学和光电子领域.     

手性有机-无机杂化氧化硅纳米管的制备

依照文献以L-苯甘氨酸为手性源合成了一个手性阴离子两亲小分子化合物.利用圆二色谱表征了该化合物水中的自组装行为.通过溶胶-凝胶复制法,以该手性两亲小分子化合物和结构助剂的组装体为模板制备了右手螺旋有机-无机杂化氧化硅纳米管.圆二色谱表征结果表明,4,4′-亚联苯基氧化硅中的联苯基团呈手性堆积.     

基于冠醚衍生物的超分子聚合物

自组装现象是生命科学最本质的内容之一,生物体系可以精确地利用非共价键相互作用形成高度有序的功能组装体.受到大自然的启发,近年来利用分子自组装构筑包括超分子聚合物在内的有序聚集体是超分子科学的研究热点.此类组装体不仅在拓扑学上具有重要的意义,而且可以用来制备动态的超分子功能材料.冠醚作为第一代超分子主体化合物,由于其结构...     

Coordination Bonds and Diels–Alder Bonds Dual Crosslinked Polymer Networks of Self‐healing Polyurethane

A dual crosslinked self‐healing polyurethane was prepared with robust mechanical properties through the dynamic reversible pyridine‐Fe³⁺ coordination bonds and Diels–Alder (DA) covalent bonds dual crosslinking strategy. Moreover, the mechanical properties and self‐healing ability of polyurethane can be tuned readily by different ratio of the coordination bonds and DA bonds. Under external load, the coordination bonds serve as sacrificial bonds are broken to dissipate energy, the DA bonds can keep the shape of sample. With the coordination bonds participation, the damaged samples can be healed under moderate heating treatment or with the aid of FeCl₃ solution. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2228–2234     

Recognition of N‐Alkyl and N‐Aryl Acetamides by N‐Alkyl Ammonium Resorcinarene Chlorides

N‐Alkyl ammonium resorcinarene chlorides are stabilized by an intricate array of intra‐ and intermolecular hydrogen bonds that leads to cavitand‐like structures. Depending on the upper‐rim substituents, self‐inclusion was observed in solution and in the solid state. The self‐inclusion can be disrupted at higher temperatures, whereas in the presence of small guests the self‐included dimers spontaneously reorganize to 1:1 host–guest complexes. These host compounds show an interesting ability to bind a series of N‐alkyl acetamide guests through intermolecular hydrogen bonds involving the carbonyl oxygen (C?O) atoms and the amide (NH) groups of the guests, the chloride anions (Cl^?) and ammonium (NH₂⁺) cations of the hosts, and also through CH ??? π interactions between the hosts and guests. The self‐included and host–guest complexes were studied by single‐crystal X‐ray diffraction, NMR titration, and mass spectrometry.     

Why do Congo Red,Evans Blue,and Trypan Blue differ in their complexation properties?

Congo Red, Evans Blue, and Trypan Blue dyes were evaluated in terms of their ability to form supramolecular systems in water solution. A geometric transformation set was defined to construct a supramolecular model system composed of eight dye molecules. The stability of the constructed multimolecular systems was estimated by molecular dynamics using AMBER 4.1 and DISCOVER force fields. The results essentially confirm the tendency toward self‐assembly in each case. However, Congo Red and Evans Blue were found to form stable, continuous, ribbon‐like supramolecular organizations, whereas Trypan Blue self‐assembly appeared defective; some additional deviations from planarity seem to be the main reason for the disturbance in self‐assembling. The extra rotation around the azo bonds in the Trypan Blue molecule is slightly extorted by the close proximity of sulfonic groups. This may also be the direct cause of the observed deviation from symmetry in the molecule of this dye. The results confirm that the self‐assembling capability of the compounds studied correlates with the capacity to complex proteins, supporting the idea that supramolecularity may create specific ligation properties. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 656–667, 2000     

The chromatographic behaviour of cycloolefins on stationary phases of different polarity. Prediction of their retention indices and boiling points

Summary The retention indices of mono and polycycloolefins with endo or exo double bonds, on squalane or polypropylenglycol 425 are related to their physico-chemical properties such as boiling point, molar volume, molar refraction, and refractive index. Equations have been empirically obtained, from which accurate retention indices of these compounds can be predicted. Unknown boiling points of some of these compounds can also be calculated from their lineal relation with the retention index on squalane.     

Iridium‐Catalyzed Synthesis of Diaryl Ethers by Means of Chemoselective CF Bond Activation and the Formation of BF Bonds

Transition‐metal‐catalyzed C? F activation, in comparison with C? H activation, is more difficult to achieve and therefore less fully understood, mainly because carbon–fluorine bonds are the strongest known single bonds to carbon and have been very difficult to cleave. Transition‐metal complexes are often more effective at cleaving stronger bonds, such as C(sp²)? X versus C(sp³)? X. Here, the iridium‐catalyzed C? F activation of fluorarenes was achieved through the use of bis(pinacolato)diboron with the formation of the B? F bond and self‐coupling. This strategy provides a convenient method with which to convert fluoride aromatic compounds into symmetrical diaryl ether compounds. Moreover, the chemoselective products of the C? F bond cleavage were obtained at high yields with the C? Br and C? Cl bonds remaining.     

Coordination Assembly of Discoid Nanoparticles

Supramolecular chemistry utilizes coordination bonds to assemble molecular building blocks into a variety of sophisticated constructs. However, traditional coordination assemblies are based on organic compounds that have limited ability to transport charge. Herein, we describe coordination assembly of anisotropic FeS₂ pyrite nanoparticles (NPs) that can facilitate charge transport. Zn²⁺ ions form supramolecular complexes with carboxylate end‐groups on NP surface, leading to multiparticle sheets with liquid‐crystal‐like organization. Conductivity and Hall carrier mobility of the p‐type layered semiconductor films with Zn²⁺ coordination bridging exceed those known for coordination compounds, some by several orders of magnitude. The nanoscale porosity of the assembled sheets combined with fast hole transport leads to high electrocatalytic activity of the NP films. The coordination assembly of NPs embraces the versatility of several types of building blocks and opens a new design space for self‐organized materials combining nanoscale and supramolecular structural motifs.     

Electronic structure and metal-metal interaction in edge- and face-sharing bioctahedral compounds of molybdenum

Ab initio configuration interaction calculations have been performed for the title compounds to study the nature of the metal-metal interaction. By analyzing the energy diagrams and the CI wave functions, it can be shown that the metal-metal interaction in such compounds has a dual nature, namely, formation of some direct metal-metal bonds and antiferromagnetic coupling of remaining electron pairs. Experimental observations of the magnetic behavior of the compounds can be explained satisfactorily by the calculated energy diagrams which include low-lying magnetic excited states as the result of the weak exchange coupling. © 1996 John Wiley & Sons, Inc.     

Cation–Cation Pairing by NCH⋅⋅⋅O Hydrogen Bonds

The pairing of ions of opposite charge is a fundamental principle in chemistry, and is widely applied in synthesis and catalysis. In contrast, cation–cation association remains an elusive concept, lacking in supporting experimental evidence. While studying the structure and properties of 4‐oxopiperidinium salts [OC₅H₈NH₂]X for a series of anions X^? of decreasing basicity, we observed a gradual self‐association of the cations, concluding in the formation of an isolated dicationic pair. In 4‐oxopiperidinium bis(trifluoromethylsulfonyl)amide, the cations are linked by N? H???O?C hydrogen bonds to form chains, flanked by hydrogen bonds to the anions. In the tetra(perfluoro‐tert‐butoxy)aluminate salt, the anions are fully separated from the cations, and the cations associate pairwise by N? C? H???O?C hydrogen bonds. The compounds represent the first genuine examples of self‐association of simple organic cations based merely on hydrogen bonding as evidenced by X‐ray structure analysis, and provide a paradigm for an extension of this class of compounds.     

沉淀聚合制备聚二乙烯基苯微粒

利用沉淀聚合方法，自由基引发二乙烯苯聚合，制备了具有较窄粒度分布的聚二乙烯基苯直发细微粒，用扫描电镜对其表面形态和粒度进行了表 征；红外光谱表明这种聚合物超微粒仍存在有较多未反应的悬吊双键，可以继续与其它功能基团进一步反应，且粒度均一可控。     

Hydrothermal Syntheses,Supramolecular Structures and the Third—order Non—linear Optical Properties of Three Copper（Ⅰ）Halide Amine Complexes Connected via Secondary Bonding Interactions

The hydrothermal reactions of CuI,KI and bidentate amines [1,10-phenanthroline(phen) or ethylenediamine (en)]gave the three copper (Ⅰ）halide compounds,Cu3I3(phen)2(1),CuI(phen)2(2) and [Cu(en)2][CuI2](3),which were struc-turally characterized via single-crystal X-ray diffraction stud-ies,Hydrogen bonds and π-π interactions are the most remarkable structural features of the title compounds .All can be described as higher-dimensional supramolecular compounds connected via these secondary bondings,Moreover,the title compounds were characterized by elemental analyses,IR spectra and TGA analyses,The third-order non-linear optical properties of the title compounds were also investigated and all exhibit nicer non-linear absorption and self-focusing performance.