杯芳烃的超分子化学

杯芳烃以其特殊的结构和易于衍生化的特点而成为继冠醚和环糊精之后的第三代超分子，它具分子自组装功能，也可以作为分子平台，并能包结，螯合客体分子。     

杯芳烃的配位化学

本文首次２报道了八对磺酸钠八羟基甲氧基杯「８」芳烃酸离解常数的测定结果，还以ＰＨ滴定法对该试剂对过滤元素的各种配合物进行了系统研究，发现此配体能形成ＭＨｎＬ型配合物。     

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.     

含有杯芳烃的树枝状分子

杯芳烃与树枝状大分子是超分子化学中两类极为重要的主体分子,将这两种主体分子结合在一起所得到的基于杯芳烃的树枝状大分子,不仅仅能够将两者的优点集中到一个分子之中,同时还有可能产生一些新颖的性能,成为新型的智能材料、分子器件或是纳米材料。本文按照杯芳烃的类型,在树枝状大分子中的位置,综述了到目前为止有关这一新型主体分子的研究成果,展望了它在将来的发展。     

糖杯芳烃的研究进展

综述了近年来一类新型分子受体——糖杯芳烃的合成以及性质方面的研究进展.     

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.     

色谱分离与第三代超分子——杯芳烃

评述了色谱在杯芳烃类化合物研究中的应用和杯芳烃类化合物在色谱中的应用，并对其在色谱中的应用前景作了展望。     

新型大环超分子化学:从杂杯芳烃到冠芳烃——纪念黄志镗先生诞辰90周年

本文介绍了杂杯芳烃和冠芳烃的研究起源,总结了杂杯芳烃和冠芳烃的设计与合成、构象和大环空腔结构特征,展示了杂杯芳烃和冠芳烃的分子识别和组装性质,概述了杂杯芳烃和冠芳烃在功能材料的制备中的应用,展望了大环超分子化学未来的发展方向。     

基于杯芳烃的分子容器的合成及其对有机铵的可逆识别

将三(吡啶基甲基)胺(TPA)引入杯芳烃的下缘, 合成了一种新的具有杯状结构的杯芳烃衍生物, 研究了其对有机铵的分子识别行为.     

磺化杯芳烃的超分子组装体构筑及其功能

磺化杯芳烃具有非常强的分子键合能力, 被广泛用于水相超分子自组装研究. 介绍了磺化杯芳烃与客体阳离子形成超分子组装体的主要驱动力和形貌调控因素; 总结了包括主体诱导客体聚集、客体诱导主体聚集及主客体共组装在内的三种主要聚集模式; 并展望了其在刺激响应材料、药物传递载体、多功能超分子平台和超分子催化等领域的重要应用前景.     

Exploiting Complementary Second-sphere Effects in Supramolecular Coordination Solids

In the design of extended supramolecular solids, reliable synthons are a valuable commodity. This work concerns the complementary second-sphere coordination interactions between a highly preorganized hexasulphonated ligand, L, and aquated metal ions. Four second-sphere inclusion complexes [M(H²O)⁶]² L ·(S)³ (M/S: Mg/acetone, 1; Zn/acetone, 2, Mg/dioxane, 3; Zn/dioxane, 4) and three extended networks {[(M(H²O)³)²(L)]·(H²O)^14.5}^∞ (M=Cr, 5; Fe, 6; Al, 7) have been structurally characterized by X-ray crystallography. The second-sphere effects on the stabilization of the primary coordination sphere are illustrated by TGA experiments. In these assemblies, the potential of a new supramolecular synthon is illustrated, that being the complementary hydrogen-bonding interaction between cis-aquo ligands and sulphonate oxygen atoms.     

超分子高分子化学进展

综述了超分子高分子化学近年来的进展,着重介绍固相聚合和毛杆高分子等方面的最新研究成果及应用展望,对超分子高分子化学的主要研究方法也作了扼要的介绍。     

典型锕系超分子组装体的构筑原理及研究进展

锕系超分子化学是锕系元素化学的重要研究领域,可以为乏燃料后处理的配位化学基础研究提供重要信息,并为探索锕系功能材料在发光、传感、催化和分离等方面的功能应用提供关键材料体系。本文介绍了基于锕系金属离子的金属-有机超分子组装体这一新兴领域的最新研究进展。从锕系超分子组装体的构筑原理出发并结合笔者自身研究情况,对基于主客体准轮烷配体的锕系-轮烷配位聚合物、具有闭合结构的锕系配位组装体和基于超分子相互作用的锕系超分子聚合物这三类典型的锕系超分子组装体的研究进展进行了梳理和总结阐述。期望为未来新型锕系超分子组装体的设计合成提供参考,促进相关领域的进步和发展。     

Molecules with Large Cavities in Supramolecular Chemistry

Supramolecular chemistry is a new area of research that has rapidly developed from pure synthetic chemistry, and its novelty has led to interdisciplinary cooperation between organic and inorganic chemistry, biochemistry, physical and theoretical chemistry, and physics. Whereas molecular chemistry essentially deals with the covalent bonding of atoms, Supramolecular chemistry is predominantly involved in the study of the weaker intermolecular interactions resulting in the association and self-organization of several components to form larger aggregates (supramolecules). The first crown ether discovered by the subsequent Nobel prizewinner Pedersen was more the fortuitous reaction product of an impurity, but nowadays, some twenty-five years later, chemists are able to tailor host molecules to special requirements. Host compounds having a cyclophane skeleton make an important contribution, since their aromatic structural units ensure the necessary rigidity of the molecular structures and thereby improve the preorganization of the coordination sites for the cooperative binding of the guests. During the course of the rapid development of Supramolecular chemistry such a large number of synthetic hosts has been developed and their interaction with guests studied in such depth that we must restrict ourselves here to a discussion of a particular group of host compounds, namely cavity-supporting macrobicyclic and macrooligocyclic phanesu, which bear a similar relation to open-chain and monocyclic hosts as the metal-complexing cryptands to the podands and crown ethers. The molecular architecture of these three-dimensionally bridged macrooligocycles is a challenge for synthetic chemistry. (Not only the size and shape of the intramolecular cavity, but also the provision of the latter with suitable coordination centers have to be included in the synthesis strategy.) The capacity for the envelopment of guests from all sides and the expedient endo functionalization often also produce a particularly strong binding of host and guest, outstanding selectivities with regards to molecular recognition, and special properties of the Supramolecular complexes.     

卤键在超分子化学中的应用进展

卤键是指作用在卤原子(路易斯酸)和具有孤对电子的原子或π电子体系(路易斯碱)之间的新型弱相互作用,其在超分子多维自组装和分子识别(如超分子催化、超分子选择拆分、超分子传感)等领域有着广泛的应用。本文介绍了卤键的类别、特性、功能及在超分子化学结构与功能领域中的应用。     

Gemini型两亲分子超分子组装研究进展

综述了国内外对Gemini型两亲分子在超分子组装方面的研究进展。总结了Gemini分子的体相组装、界面组装以及近几年应用领域的研究进展;着重介绍了基因传递、纳米材料模板、降解剂、药物缓释以及胶凝剂的制备等方面的应用进展;对相关研究领域的主要研究成果做了一些探讨和分析;为更加深入探索和研究Gemini型两亲分子的超分子组装提供参考信息。     

The Coordination Chemistry of Multidentate Isocyanide Ligands

In spite of the excellent ligation properties of isocyanides, until a few years ago there was only a small number of known multidentate ligands of this type. One of the reasons for this lack of interest, when compared to monodentate isocyanides, was the linear arrangement of the M? C?N? R group, which usually inhibits the formation of mononuclear chelate complexes and leads to the formation of multinuclear or polymeric metal complexes. In these, the multidentate ligand acts in a monodentate fashion towards each metal atom. Only recently has a series of polyisocyanides with large ligand backbones been synthesized successfully. Bidentate isocyanides can bridge two metal atoms or react to give chelates with only one metal center. Tripodal ligands form mono- or binuclear complexes, in which the largest organometallic rings observed to date occur (up to 36 atoms). This class of ligands promises to be interesting for the synthesis of stable, diagnostically important technetium complexes of the type [Tc(CNR) ₆ ]⁺. There also appear to be applications for tripodal isocyanides in catalysis. A facial, chiral Cr(CNR^*)₃ unit might be able to catalyze the hydrogenation or isomerization of prochiral double bonds. It is even possible to bind triisocyanides with suitable backbones to carbonyl trimetal clusters, thereby stabilizing them, or making selective cluster formation possible. Coordinated isocyanides can be transformed readily into carbene ligands, which, in the future, could lead to complexes with polycarbene ligation.     

Supramolecular Chemistry In Silico

Computational protocols capable of modelling supramolecular complexes have been evaluated. The complexation of cations by crown ethers and quaternary ammonium ions by an oxacalix[3]arene are presented as examples. In the latter case reliable qualitative results were obtained using the semi-empirical PM3 method where guest LUMO and electrostatic potential energies have been shown to correlate with experimental binding data. The optimal method for more accurate results combines semi-empirical equilibrium geometry and property calculations with single point energy calculations at the HF/6–31G* or BP/6–31G* quantum mechanical level.     

超分子化学在药物共晶中的应用

药物共晶是一种新兴的药物晶型, 一个给定的活性药物分子通过形成共晶, 一方面可以大大丰富其结晶形式, 另一方面可以改善其物化性质及临床疗效. 本文从超分子化学的角度对药物共晶进行了综述, 列举了一系列通过氢键超分子合成子进行药物共晶设计和制备的研究实例, 旨在促进超分子化学和药学的交叉融合.     

Straightforward Preparation of a Solid-state Luminescent Cu11 Polymetallic Assembly via Adaptive Coordination-driven Supramolecular Chemistry

The tridentate dpmp ligand was reacted with Cu^I salt and cyano ligand affording selectively and unexpectedly the polymetallic Cu₁₁ complex 2 along one-step reaction. The formation of this derivative 2 can be explained by self-assembling processes controlled by adaptive coordination-driven supramolecular chemistry. The solid-state photophysical behavior of 2 was studied suggesting TADF properties.