超分子砌块间苯二酚杯芳烃的研究进展

间苯二酚杯芳烃是一类以间苯二酚为单元的杯芳烃, 作为新一代超分子砌块, 在分子催化、分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用, 已成为当今化学研究的新热点. 综述了间苯二酚杯芳烃的功能化修饰及其应用新进展.     

一类新型超分子主体——硫代杯芳烃的研究进展

硫代杯芳烃是一类以硫原子取代桥联亚甲基的新型杯芳烃, 作为新一代超分子砌块, 在分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用, 已成为当今超分子化学研究的新热点. 综述了硫代杯芳烃及其衍生物的合成、功能化修饰及应用方面的研究进展.     

杯芳烃超分子医学

超分子医学是利用超分子化学的理念为现代医药学服务.杯芳烃作为重要的人工大环受体分子,在超分子化学和超分子医学的发展中均扮演着重要角色.本文介绍了超分子医学和杯芳烃的基本概念和发展概况,总结了我们在杯芳烃超分子医学包括疾病诊断、生物成像、药物研发和药物递送等方面取得的进展,还兼顾了其他课题组的代表性成果,最后思考了杯芳烃在现代医药学领域如何健康有序的发展,展望了杯芳烃超分子医学未来的发展前景和应用价值.     

基于杯芳烃主体的分子自组装研究进展

分子自组装是超分子化学最重要的研究内容之一. 杯芳烃作为继冠醚、环糊精之后的第三代人工合成受体分子已在分子自组装研究方面取得了重要进展并显示了广泛的应用前景. 主要综述杯芳烃衍生物通过氢键、金属诱导配位、π-π作用、疏水作用等非共价键弱相互作用力在溶液状态、固态和界面的分子自组装方面的研究进展.     

间苯二酚杯芳烃——化学家的建筑积木

间苯二酚杯芳烃是超分子化学的第3代主体分子。介绍了间苯二酚杯芳烃的结构、衍生化途径及其衍生物的用途。     

桥联杯[6]芳烃研究进展

综述了桥联杯[6]芳烃的合成及构象固定等方面的研究进展,并以下缘1,4位桥联杯[6]芳烃,杯[6]冠醚和杯[6]穴醚及其类似物等主体分子为重点,综述了桥联杯[6]芳烃在分子识别和超分子化学领域中的应用研究的最新进展。     

杯芳烃促进的过渡金属催化反应

近年来,过渡金属催化反应已经成为有机化学中构建碳碳键和碳杂原子键的最有效方法之一,并引起了化学家的极大研究兴趣.杯芳烃是继冠醚和环糊精之后的第三代超分子主体化合物,其配位性能一直是超分子化学研究的热点.通过对其下缘的酚羟基、上缘的苯环对位以及连接苯环单元的亚甲基进行设计改造,杯芳烃可以有效地作为过渡金属催化剂的配体,或者与过渡金属正离子组装成为新的过渡金属催化剂,从而高效地促进反应的进行.主要介绍了近十年来,杯芳烃作为不同过渡金属催化剂的配体并用于各种过渡金属催化反应的研究进展.     

杯吡咯和杂杯吡咯的结构、合成与应用

杯吡咯以其特殊的结构和优异性能, 在主客体化学尤其是分子识别等方面的应用前景已备受关注, 合成新型功能化杯吡咯及其衍生物已成为超分子化学领域的研究热点之一. 近年来通过引入新型芳烃基体合成了结构和性能多样的杂杯吡咯. 主要介绍了功能化的杯吡咯和杂杯吡咯的结构、合成及其在分子识别等领域的应用.     

杯芳烃在液相色谱、毛细管电泳和电色谱中的应用进展

利用杯芳烃的分子识别作用提高色谱分离选择性是超分子化学在分离科学中的成功应用.本文从杯芳烃分离材料的制备、分离机理和应用等,综述了近年来杯芳烃在液相色谱、毛细管电泳和电色谱中的研究进展.     

含杂原子杯芳烃的合成研究进展

综述了含杂原子杯芳烃的结构、命名方法、合成方法等方面的研究进展.指出在超分子化学领域,杯芳烃骨架结构的改变是杯芳烃研究的热点之一;与传统杯芳烃相比,在杯芳烃分子骨架中引入桥联杂原子或芳杂环后,不仅使得其在结构和分子识别方面产生新颖变化,而且使得其合成方法也发生巨大改变.     

Hierarchical assembly of uranyl metallacycles involving macrocyclic hosts

Actinide metallacycles are an emerging class of functional coordination assemblies, but multi-level assembly from metallacycle units toward hierarchical supramolecular structures are still rarely investigated. In this work, we put forward a novel supramolecular inclusion-based method through introducing two macrocyclic hosts, cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) to facilitate hierarchical assembly of uranyl metallacycles with higher complexity, and successfully prepare two different kinds of uranyl metallacycle-based complexes with intriguing hierarchical structures, a CB[7]-based four-member molecular necklace ([4]MN) and a CB[8]-involved ring-in-ring supramolecular polymer chain. The results obtained here prove the feasibility of supramolecular inclusion for regulating coordination assembly of uranyl metallacycles and related hierarchical structures. It is believed that this method can be used to achieve the construction of actinide coordination assemblies with higher structural complexity.     

Supramolecular Coordination Cages for Asymmetric Catalysis

Inspired by the high efficiency and specificity of enzymes in living systems, the development of artificial catalysts intrinsic to the key features of enzyme has emerged as an active field. Recent advances in supramolecular chemistry have shown that supramolecular coordination cages, built from non-covalent coordination bonds, offer a diverse platform for enzyme mimics. Their inherent confined cavity, analogous to the binding pocket of an enzyme, and the facile tunability of building blocks are essential for substrate recognition, transition-state stabilization, and product release. In particular, the combination of chirality with supramolecular coordination cages will undoubtedly create an asymmetric microenvironment for promoting enantioselective transformation, thus providing not only a way to make synthetically useful asymmetric catalysts, but also a model to gain a better understanding for the fundamental principles of enzymatic catalysis in a chiral environment. The focus here is on recent progress of supramolecular coordination cages for asymmetric catalysis, and based on how supramolecular coordination cages function as reaction vessels, three approaches have been demonstrated. The aim of this review is to offer researchers general guidance and insight into the rational design of sophisticated cage containers for asymmetric catalysis.     

Bis-(thiosemicarbazonato) Zn(II) complexes as building blocks for construction of supramolecular catalysts

In this paper we report the application of bis-(thiosemicarbazonato) Zn(II) complexes as building blocks in the construction of supramolecular transition metal assemblies. We investigated their coordination behaviour towards pyridylphosphine molecules and found these systems comparable to those based on Zn(porphyrin) and Zn(salphen) complexes. Additionally, catalytic experiments and an in situ high-pressure FTIR study of the supramolecular rhodium hydroformylation catalysts, assembled using the bis-(thiosemicarbazonato) Zn(II) complexes, demonstrate their applicability in supramolecular catalysis and their potential for application in other areas of supramolecular chemistry.     

Shape‐Persistent Organic Cage Compounds by Dynamic Covalent Bond Formation

One area of supramolecular chemistry involves the synthesis of discrete three‐dimensional molecules or supramolecular aggregates through the coordination of metals. This field also concerns the chemistry of supramolecular cage compounds constructed through the use of such coordination bonds. To date, there exists a broad variety of supramolecular cage compounds; however, analogous organic cage compounds formed with only covalent bonds are relatively rare. Recent progress in this field can be attributed to important advances, not least the application of dynamic covalent chemistry. This concept makes it possible to start from readily available precursors, and in general allows the synthesis of cage compounds in fewer steps and usually higher yields.     

Role of solvents in coordination supramolecular systems

Solvent effect is a vital subject in the domain of coordination chemistry. In this connection, previous researches mainly focus on the role of solvents in reaction kinetics and thermodynamics during the coordination processes. In virtue of the recent efforts on coordination supramolecular systems, especially coordination polymers or metal-organic frameworks, this feature article aims to demonstrate the solvent effect on regulating such diversiform metallosupramolecular solids, incorporating their crystal growth/assembly, structural modulation, dynamic transformations, and potential applications, which may provide new insights into the rational design and construction of such advanced crystalline materials.     

Luminescent Metallo‐Supramolecular Polymers

Luminescent metallo‐supramolecular polymers are a type of functional supramolecular architectures which integrates the advantages of emission, metal‐coordination, supramolecular chemistry as well as polymeric properties to realize advanced functions. Due to the abundant stimuli‐responsiveness of supramolecular assemblies and the light‐emitting properties, they have been widely applied as chemo‐sensors, light‐emitting devices, contrast agents for bio‐imaging, etc. In this review, we classify luminescent metallo‐supramolecular polymers based on the types of species (lanthanides, organometallic compounds, oligomer or polymer‐based ligands, small‐molecule‐based organic ligands) used to generate the luminescence and summarize recent developments of luminescent metallo‐supramolecular polymers. We mainly focus on the functions and applications of luminescent metallo‐supramolecular polymers and hope to give our reader a snapshot of research on luminescent metallo‐supramolecular polymers and encourage more scientists to devote into this promising area.     

稀土超分子配合物研究进展

超分子化学作为"广义上的配位化学",是一个充满活力的领域。基于配位自组装,设计合成具有不同拓扑结构和功能特性的超分子配合物是超分子化学的研究重点。基于稀土元素构筑的超分子配合物不仅丰富了配位超分子体系,也是制备功能性配合物的核心内容。主要从拓扑结构调控、结构修饰和功能特性等方面综述了螺旋、格子、环状和笼状等稀土超分子配合物的最新研究进展,探讨了配体设计在超分子自组装过程中的作用,旨在为稀土超分子化合物的设计与调控提供新思路。     

阴离子在构筑配位聚合物网络结构中的作用

本文结合近年来我们的研究工作及国内外相关研究进展，概述了利用金属离子和简单有机配体通过配位自组装构筑配位聚合物过程中阴离子因素的作用，并进一步展望了今后的研究和发展方向。     

The Assembly of Supramolecular Boxes and Coordination Polymers Based on Bis‐Zinc‐Salphen Building Blocks

We report the assembly of supramolecular boxes and coordination polymers based on a rigid bis‐zinc(II)‐salphen complex and various ditopic nitrogen ligands. The use of the bis‐zinc(II)‐salphen building block in combination with small ditopic nitrogen ligands gave organic coordination polymers both in solution as well as in the solid state. Molecular modeling shows that supramolecular boxes with small internal cavities can be formed. However, the inability to accommodate solvent molecules (such as toluene) in these cavities explains why coordination polymers are prevailing over well‐defined boxes, as it would lead to an energetically unfavorable vacuum. In contrast, for relatively longer ditopic nitrogen ligands, we observed the selective formation of supramolecular box assemblies in all cases studied. The approach can be easily extended to chiral analogues by using chiral ditopic nitrogen ligands.     

Coordination motifs in modern supramolecular chemistry

In this paper we describe the contribution of coordination chemistry to the creation and development of supramolecular chemistry. Both discrete- and infinite buildups are examined. The first group comprises metal-containing host molecules and organic acceptors for metal cations; the second includes coordination polymers, ionic -and liquid crystals. Their potential- and practical applications are briefly explained.