超分子有机膦大环化合物研究进展

有机膦大环化合物是伴随着大环化学的出现而发展起来的．它们不仅具有多变的结构而且非常稳定;不仅能够包结客体分子,还可以与许多过渡金属形成稳定的配位化合物,在主客体化学以及金属有机催化领域中受到人们的广泛关注．由于其独特的性质,有机膦大环化合物在超分子化学的发展中具有重要的地位．本文主要介绍了近些年有机膦大环化合物研究的新进展及其在超分子化学中的应用．     

Controllable macrocyclic supramolecular assemblies in aqueous solution

A series of macrocycles, including crown ethers, cyclodextrins, calixarenes, pillararenes and cucurbiturils, are well known to be able to associate various organic/inorganic/biological guest molecules and ions in their well-defined cyclic cavities to form stable host-guest complexes and supramolecular systems through the cooperative contributions of various non-covalent interactions. When one or more functional groups are attached to the cavity of macrocycles or guest molecules, enhanced and/or controlled host-guest associations may take place, leading to not only improved host-guest binding abilities but also fascinating properties. In this review, some representative contributions in the construction of controllable macrocyclic supramolecular assemblies in aqueous solution are presented with an emphasis on the stimuli-responsive control manner and wide applications of this property.     

Conjugated macrocycles: concepts and applications

One of the most important objectives in materials, chemical, and physical sciences is the creation of large conjugated macrocycles with well-defined shapes, since such molecules are not only theoretically and experimentally interesting but also have potential applications in nanotechnology. Fully unsaturated macrocycles are regarded as models for infinitely conjugated π systems with inner cavities, and exhibit unusual optical and magnetic behavior. Macrocycles have interior and exterior sites, and site-specific substitution at both or either site can afford attractive structures, such as 1D, 2D, and 3D supramolecular nanostructures. These nanostructures could be controlled through the use of π-extended large macrocycles by a bottom-up strategy. Numerous shape-persistent π-conjugated macrocycles have been synthesized, but only a few are on the nanoscale. This Review focuses on nanosized π-conjugated macrocycles (>1 nm diameter) and giant macrocycles (>2 nm diameter), and summarizes their syntheses and properties.     

Double armed crown ethers and armed macrocycles as a new series of metal-selective reagents: a review

Various double armed crown ethers and related macrocycles are presented as metal-selective reagents characterized by macrocyclic ligands and metal-ligating sidearms. They exhibit unique metal binding and recognition functions via macroring-sidearm cooperative action. Since they form three dimensional complexes suitable for metal-sensing and separation, we can develop a new series of metal-selective reagents via armed macrocycle strategy. Polymerization and immobilization of the armed macrocycles further enhance the usefulness in analytical science. This review focuses primarily on the molecular design, host-guest chemistry, and analytical applications of the armed macrocycles, and clearly indicates that these macrocycles provide new options in designing a metal-selective reagent.     

Synthesis,structure and catalysis/applications of <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene based on macrocycles

It is well-recognized that N-heterocyclic carbenes (NHCs) ligands have provided a new dimension to the design of catalysts. Macrocyclic molecules are a class of material chemistry and have served as the synthetic hosts, and molecular recognition. In recent years, researchers have moved toward fabricating interlocking molecules with specific structures and properties. Therefore, researchers have developed more macrocycles complex based NHCs with multi-complexation modes that provide more diverse host–guest systems. In this account, this review highlights recent advances on synthesis, structure and applications of NHC based on macrocycles. According to the structure of different macrocycles, the complexes can be divided into four parts: (i) complexes of NHC based on crown ether; (ii) complexes of NHC based on porphyrin; (iii) complexes of NHC based on calixarene; (iv) complexes of NHC based on the other macrocycles. The complexes showed good coordination ability with different metal ions and showed excellent catalyst activity and optical ability.     

“Texas-Sized” Molecular Boxes: From Chemistry to Applications

The design and synthesis of novel macrocyclic host molecules continues to attract attention because such species play important roles in supramolecular chemistry. However, the discovery of new classes of macrocycles presents a considerable challenge due to the need to embody by design effective molecular recognition features, as well as ideally the development of synthetic routes that permit further functionalization. In 2010, we reported a new class of macrocyclic hosts: a set of tetracationic imidazolium macrocycles, which we termed “Texas-sized” molecular boxes (TxSBs) in homage to Stoddart’s classic “blue box” (CBPQT⁴⁺). Compared with the rigid blue box, the first generation TxSB displayed considerably greater conformational flexibility and a relatively large central cavity, making it a good host for a variety of electron-rich guests. In this review, we provide a comprehensive summary of TxSB chemistry, detailing our recent progress in the area of anion-responsive supramolecular self-assembly and applications of the underlying chemistry to water purification, information storage, and controlled drug release. Our objective is to provide not only a review of the fundamental findings, but also to outline future research directions where TxSBs and their constructs may have a role to play.     

Applications of pillarenes,an emerging class of synthetic macrocycles

Synthetic macrocycles, a typical type of building block for molecular recognition and self-assembly, are crucial to supramolecular chemistry and materials science. Since 2008, a new generation of synthetic macrocyclic hosts, pillarenes and their abundant derivatives, which consist of hydroquinone units linked by methylene bridges at 2,5-positions, have been the focus of much research. Numerous studies on their host-guest properties and the fabrication of supramolecular assemblies have demonstrated that pillarenes and their derivatives possess many advantages that facilitate their applications in many research fields. Herein we summarize and classify the applications of pillarenes in terms of artificial transmembrane channels, controlled delivery systems, dispersion of carbon hybrid materials, extraction and absorption, liquid crystals, metal-organic frameworks, sensing and detection, stabilization of nanoparticles (Au/Ag/CdTe), and other typical biological applications. We also provide an overview of future developments in pillarene chemistry.     

Selenium containing macrocycles:transformation between Se-N/Se-S/Se-Se bonds

Macrocycles possess potential applications in supramolecular chemistry and biosystems.Thus development of new kinds of macrocycles is of significance.Herein,novel macrocycles containing Se-Se/Se-S bonds were synthesized via transformation between selenium related dynamic covalent bonds.A monomer containing two ebselen moieties was synthesized(M1).The Se-N bonds in M1 were reduced by dithiothreitol,forming Se-S linked dimer(D1).To realize the transformation from Se-S bonds to Se-Se bonds,guest molecules were added as template,triggering the formation of Se-Se linked dimer(D2).The formation of these two new kinds of macrocycles was determined by ~1H NMR and ~(77)Se NMR,and the necessity of guest molecules was also confirmed.The introduction of ebselen moieties and Se-S bonds or Se-Se bonds into macrocycles may endow it with new responsiveness and bioactivities,as well as new types of host-guest chemistry.     

稀土/L型沸石主-客体发光功能材料的研究进展

沸石微孔晶体材料作为客体功能物种的主体材料在主-客体组装化学中发挥着越来越重要的作用,在微型激光器、非线性光学、生物成像、光放大及光显示等高技术领域已显示出广阔、诱人的发展前景.本文介绍国内外,特别是河北工业大学在稀土/L型沸石主-客体杂化功能材料的组装、结构及其发光性能的研究工作,具体包括：稀土有机配合物在L沸石孔道内的组装、L型沸石-有机高分子透明杂化发光材料的制备及稀土有机配合物诱导控制的L型沸石自组装等.此外,本文对稀土/L型沸石主-客体杂化发光功能材料的研究进行了展望.     

Recent advances of folded tetraphenylethene derivatives featuring through-space conjugation

Through-space conjugated molecules are interesting building blocks for the construction of functional materials that allow multi-dimensional transport of carrier and energy. However, the well explored through-space conjugated molecules are quite limited, which defers their structure-property correlation establishment and wide-scale application. In this review, we introduce a kind of newly-emerging folded tetraphenylethene derivatives featuring through-space conjugation. Their synthesis, crystal and electronic structures, and optical properties are described, and their representative applications as bipolar charge-transporting materials in organic light-emitting diodes and as single-molecule wires in molecular devices are presented, which are anticipated to provide guidance for the further expansion of through-space conjugated systems.     

Coronarenes: recent advances and perspectives on macrocyclic and supramolecular chemistry

Synthetic macrocyclic host molecules always play an essential role in the establishment and development of supramolecular chemistry. Along with the continuous interests in the study of classical macrocycles, recent decades have witnessed the emergence and rapid development of the chemistry and supramolecular chemistry of novel and functional macrocycles. Owing to their easy availability, a self-tunable V-shaped cavity resulted from 1,3-alternate conformation, and diversified electronic features steered by the interplay between heteroatom linkages and aromatic rings, heteracalixaromatics act as a type of versatile and powerful macrocyclic hosts in molecular recognition and fabrication of supramolecular systems. Very recently, by means of engineering the bond connectivity or the recombination of chemical bonds within heteracalixaromatics, we have devised coronarenes, a new generation of macrocycles. In this concise review, macrocyclic and supramolecular chemistry of coronarenes are summarized in the order of their syntheses, structural features, molecular recognition and self-assembly properties. In the last part of this article, personal perspectives on the study of macrocyclic and supramolecular chemistry will also be discussed.     

Water-soluble pillar[4]arene[1]quinone: Synthesis,host-guest property and application in the fluorescence turn-on sensing of ethylenediamine in aqueous solution,organic solvent and air

Water-soluble pillar[5]arenes are a class of typical macrocycles and have aroused tremendous attention for its easy to modify, abundant host-guest properties and extensive applications. However, up to now, all the reported water-soluble pillar[5]arenes acted as the host molecules, whereas they failed to be postsynthetically modified, which seriously impeded the development of the pillar[5]arene-based supramolecular chemistry. In this work, a new water-soluble pillar[5]arene, pillar[4]arene[1]quinone, was designed and synthsized with eight quaternary ammonium groups as well as a quinone units. Such a new water-soluble pillar[4]arene[1]quinone was capable of forming 1:1 stable complex with sodium 1-octanesulfonate in aqueous solution. Since the 1,4-quinone unit of WP[4]Q[1] could react with ethylenediamine (EDA) to form a conjugated quinoxaline structure, so pillar[4]arene[1]quinone could apply to the facile fluorescence turn-on sensing of EDA in aqueous solution, organic solvent and air.     

共轭聚合物荧光纳米粒子研究进展

近年来,共轭聚合物荧光纳米粒子因其优异的光学性能,在化学、医学和环境科学等研究领域显示了极其广阔的应用前景.相比于传统无机半导体荧光纳米材料,共轭聚合物荧光纳米粒子具有结构多样性、功能可设计性、生物相容性好等显著优势.本文从共轭聚合物荧光粒子的制备方法、光学性能、表面功能化修饰出发,重点讨论了近年来共轭聚合物纳米粒子作为荧光探针在细胞成像及生物化学检测方面的研究进展,阐述了当前研究的主要发展方向和仍需解决的问题.     

Advances in the study of the host-guest interaction by using coronene as the guest molecule

This review supplied direct insight of host-guest molecule system by using COR as the guest molecule.     

Macrocycle-Based Crystalline Supramolecular Assemblies Built with Intermolecular Charge-Transfer Interactions

Synthetic macrocycles have served as principal tools for supramolecular chemistry, have greatly extended the scope of organic charge transfer (CT) complexes, and have proved to be of great practical value in the solid state during the past few years. In this Minireview, we summarize the research progress on the macrocycle-based crystalline supramolecular assemblies primarily driven by intermolecular CT interactions (a.k.a. macrocycle-based crystalline CT assemblies, MCCAs for short), which are classified by their donor–acceptor (D-A) constituent elements, including simplex macrocyclic hosts, heterogeneous macrocyclic hosts, and host–guest D-A pairs. Particular attention will be focused on their diverse functions and applications, as well as the underlying CT mechanisms from the perspective of crystal engineering. Finally, the remaining challenges and prospects are outlined.     

铌多酸三维框架材料的研究进展

铌多酸三维框架材料是近年来无机合成化学与材料化学领域的研究热点. 该类材料不但可以将铌多酸的优异特性与框架结构的优点复合起来, 而且在光催化、 主客体化学、 能源转化等领域具有重要的应用前景. 本文总结了近10年来铌多酸三维框架材料的研究进展, 包括了该类材料的合成策略、 结构调控、 性质及应用探索. 此外, 还对当前该类材料的发展所面临的挑战进行了总结, 并对其发展前景进行了展望.     

Review: Lanthanide coordination chemistry: from old concepts to coordination polymers

Because of their remarkable and unmatched optical and magnetic properties, the lanthanides are under the limelight when it comes to high technology. These elements are used in strategic applications such as optical glasses and lasers, telecommunications, lighting and displays, magnetic materials, hard-disk drives, security inks and counterfeiting tags, catalysis, biosciences, and medicine, to name but a few. Long considered as minor actors in transition metal chemistry, they have now gained respect from coordination chemists who insert them into sophisticated functional and polyfunctional molecules and materials. This mini review focuses on trivalent lanthanide ions and first summarizes their basic properties. Then some classical aspects of their coordination chemistry are discussed, followed by macrocyclic chemistry, supramolecular chemistry, and self-assembly processes. The last part of this contribution deals with coordination polymers and hybrid materials including potential applications.     

Liquid crystalline order from ortho-phenylene ethynylene macrocycles

Triangular ortho-phenylene ethynylene (o-PE) cyclic trimers represent a novel member of shape-persistent macrocycles. Shape-persistent cyclic structures remain of great interest as molecular components in the fields of supramolecular materials, host-guest chemistry, and materials science. Novel discotic liquid crystalline properties are reported from triangular-shaped o-PE macrocycles containing branched alkoxy- and/or triethylene glycol (TEG) side chains using polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). The macrocycles self-assemble into thermotropic rectangular columnar (Colr) (for M1), hexagonal columnar (Colh) (for M2), and discotic nematic (for M3) mesophases at room temperature. This work shows clearly that electron-rich PE macrocycles can form LC materials. Alkyl side chains in M1 promote order, while hydrophilic side chains of M2 generate an amphiphilic structure that provides a different driving force for organization. The ability to create ordered self-assembling materials from these novel electron-rich macrocycles is important in nanotechnology.     

Porphyrins as Molecular Electronic Components of Functional Devices

The proposal that molecules can perform electronic functions in devices such as diodes, rectifiers, wires, capacitors, or serve as functional materials for electronic or magnetic memory, has stimulated intense research across physics, chemistry, and engineering for over 35 years. Because biology uses porphyrins and metalloporphyrins as catalysts, small molecule transporters, electrical conduits, and energy transducers in photosynthesis, porphyrins are an obvious class of molecules to investigate for molecular electronic functions. Of the numerous kinds of molecules under investigation for molecular electronics applications, porphyrins and their related macrocycles are of particular interest because they are robust and their electronic properties can be tuned by chelation of a metal ion and substitution on the macrocycle. The other porphyrinoids have equally variable and adjustable photophysical properties, thus photonic applications are potentiated. At least in the near term, realistic architectures for molecular electronics will require self-organization or nanoprinting on surfaces. This review concentrates on self-organized porphyrinoids as components of working electronic devices on electronically active substrates with particular emphasis on the effect of surface, molecular design, molecular orientation and matrix on the detailed electronic properties of single molecules.     

Reporters in the nanoworld: diffusion of single molecules in mesoporous materials

Mesoporous materials have a high potential for a number of different applications in Materials Science such as in molecular sieving, as masks for the formation of nanometre-sized metallic wires, as novel drug-delivery systems or as advanced host systems for catalysis. For many of these applications a thorough understanding of the interaction of guest molecules within the host matrix is required. In this tutorial review, we cover recent single-molecule experiments that allow the investigation of host-guest dynamics with unprecedented detail. We will show how molecules diffusing in samples with (almost) perfect domain ordering still show a large heterogeneity in their mobility and interaction with the host. With the presented methodology it is now possible to dramatically improve our understanding of host-guest interactions and in return develop new nano-structured mesoporous materials with properties optimised for a certain application.