2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M(H₂O)4(Q[5])]·(NDA)}·x H₂O(M=Co (1)、Ni (2)、Zn (3))和{[Cd2Cl2(H₂O)4(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1～3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1～4中,配体2,7-H2NDA均全脱质子,形成2,7-NDA2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成...     

2，7-萘二磺酸导向构筑的五元瓜环-碱金属及碱土金属基超分子自组装体及其溶剂识别

以2,7-萘二磺酸（2,7-H₂NDA）作为结构导向剂,与五元瓜环（Q[5]）和碱金属、碱土离子（K⁺、Rb⁺、Mg²⁺、Ca²⁺）在水热条件下制备出了4种新颖的Q[5]基超分子自组装体[K₂（H₂O）₄（Q[5]）]（2,7-NDA）·4H₂O （1）、[Rb₂（H₂O）₅（Q[5]）]（2,7-NDA）·3H₂O （2）、[Mg （H₂O）₄（Q[5]）]（2,7-NDA）·8H₂O （3）和[Ca （H₂O）₄（Q[5]）]（2,7-NDA）·10H₂O （4）。单晶X射线衍射测试结果表明,自组装体1和2具有相同的结构： Q[5]分子与金属离子配位形成的是“分子胶囊”;而在3中Q[5]与Mg²⁺配位形成的是1：1型简单配合物结构;在自组装体4中,Q[5]与Ca²⁺配位形成的是一维Q[5]-Ca²⁺配位聚合物链结构。这些结构中2,7-NDA^2-阴离子平衡了体系电荷,且通过其与瓜环外壁之间的弱相互作用,促进自组装体最终构筑成三维超分子结构。此外,还研究了自组装体4的溶剂识别荧光传感性能,结果表明其能够作为有机溶剂丙酮和DMF的猝灭型荧光探针。     

五元瓜环与钕离子在四氯酸锌离子诱导下构筑的配合超分子自组装

在四氯酸锌离子诱导下,五元瓜环能与钕离子构筑形成二维配合超分子自组装。在HCl介质中,Zn²⁺容易形成四氯酸锌离子,在其诱导作用下,钕离子和五元瓜环端口羰基氧直接配位形成二维超分子自组装体。结果表明锌离子作为一种结构导向剂在形成瓜环基超分子自组装体中起到重要作用。     

五元瓜环与钕离子在四氯酸锌离子诱导下构筑的配合超分子自组装

在四氯酸锌离子诱导下,五元瓜环能与钕离子构筑形成二维配合超分子自组装。在HCl介质中,Zn2+容易形成四氯酸锌离子,在其诱导作用下,钕离子和五元瓜环端口羰基氧直接配位形成二维超分子自组装体。结果表明锌离子作为一种结构导向剂在形成瓜环基超分子自组装体中起到重要作用。     

六元瓜环与配位聚合物[Cd(H2O)3 Cl(4-PCA)]的超分子自组装及光催化性能

本文用水热法合成得到一个六元瓜环(Q[6])与一氯三水(4-吡啶甲酸)合镉(Ⅱ)配位聚合物自组装作用形成的超分子自组装体Q[6]·[Cd(H_2O)_3Cl(4-PCA)]_2·22(H_2O)。自组装体的形成源于瓜环的外壁作用,即Q[6]正电性静电势外壁与配位聚合物中4-吡啶甲酸吡啶环和配位Cl~-离子间的超分子相互作用,以及配位聚合物镉(Ⅱ)离子上配位水分子与瓜环端口羰基氧原子间的氢键作用。该自组装体对溶液中染料具有吸附作用和光催化降解的性能。     

在四氯合锌离子诱导下反式六元瓜环与碱金属离子构筑的配位超分子自组装体

在盐酸介质中,通过四氯合锌离子诱导,碱金属离子能与反式六元瓜环端口羰基氧原子直接配位构筑形成超分子自组装体。单晶结构表明在HCl介质中,四氯合锌离子形成“蜂巢结构”,而且在[ZnCl₄]^2-诱导作用下,碱金属离子和反式六元瓜环端口羰基氧直接配位形成一维超分子自组装体而填充在“蜂巢结构”中。     

在四氯合锌离子诱导下反式六元瓜环与碱金属离子构筑的配位超分子自组装体

在盐酸介质中,通过四氯合锌离子诱导,碱金属离子能与反式六元瓜环端口羰基氧原子直接配位构筑形成超分子自组装体。单晶结构表明在HCl介质中,四氯合锌离子形成"蜂巢结构",而且在[ZnCl₄]^2-诱导作用下,碱金属离子和反式六元瓜环端口羰基氧直接配位形成一维超分子自组装体而填充在"蜂巢结构"中。     

七元瓜环与N,N’-二甲基-苯甲基-1,10-二氨基癸烷的超分子自组装

设计合成了具有多个作用位点的长链分子N,N’-二甲基-苯甲基-1,10二氨基癸烷(C10DA)并将其作为客体,利用1H NMR、紫外吸收光谱及荧光光谱等手段考察了C10DA与七元瓜环(主体)的相互作用,以及形成的主客体包结配合物的结构特征.结果表明,随着主客体摩尔比的变化,其作用模式从类轮烷型包结配合物转变成哑铃型包结配合物,这一特性在分子器件的制备方面具有潜在的应用前景.     

对称二环己基取代六元瓜环与3-吡啶甲酰肼的超分子自组装

本工作以对称二环己基取代六元瓜环(CyH2Q[6])为主体分子,3-吡啶甲酰肼(NH)为客体分子,利用核磁共振(1H NMR)、等温滴定量热(ITC)、基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)研究客体分子与瓜环在水溶液中形成的物质的量比为1∶1的稳定配合物;用X-射线单晶衍射可以观察到客体分子通过离子-偶...     

对称四甲基六元瓜环与1-丁基-4,4’-联吡啶的超分子自组装

设计合成了客体分子1-丁基-4,4’-联吡啶溴化物(BV+),利用核磁共振、紫外-可见吸收光谱、热重分析及X射线单晶衍射研究其与对称四甲基六元瓜环(TMeQ[6])的超分子自组装及形成的主客体包结配合物的结构特征.结果表明,在溶液中及固体状态下,TMeQ[6]均包结BV+的烷基链部分形成1∶1包结配合物.     

Synthesis and Crystal Structure of Macrocyclic Cavitand Cucurbit[5]uril and Its Supramolecular Adduct with Cu（Ⅱ）

The first supramolecular adduct (H₃O)₂[Cu(H₂O)₄](SO₄)₂·2(C₃₀H₃₀N₂₀O₁₀)·₂₄(H₂O) based on cucurbit[5]uril was synthesized and characterized by single crystal X‐ray diffraction analysis. In the adduct, copper ion is coordinated by four oxygen atoms from H₂O. The latter links two cucurbit[5]uril molecules due to a complicated hydrogen bonding containing lattice water molecules.     

Synthesis of Cucurbit[5]uril-Spermine-[2]Rotaxanes

Cucurbit[5]uril and decamethylcucurbit[5]uril are cyclic pentamers built from glycoluril or dimethylglycoluril respectively. Two different experimental methods have been used for the synthesis of the different [2]rotaxanes. The formed rotaxanes are characterized using ¹H-NMR spectroscopy, mass spectrometry and elemental analysis. In contrast to cucurbit[5]uril no [2]rotaxane could be obtained with decamethylcucurbit[5]uril.     

Cucurbit[5]uril, Decamethylcucurbit[5]uril and Cucurbit[6]uril. Synthesis, Solubility and Amine Complex Formation

A simple way to prepare cucurbit[5]uril is described. The macrocycles of the cucurbituril type are nearly insoluble in water. The solubilities of cucurbit[5]uril, decamethylcucurbit[5]uril and cucurbit[6]uril in hydrochloric acid, formic acid and acetic acid of different concentrations have been investigated. Due to the formation of complexes between cucurbit[n]urils and protons the solubility increases in aqueous acids. The macrocyclic ligands are able to form complexes with several organic compounds. Thus, the complex formation of the cucurbituril macrocycles with different amines has beenstudied by means of calorimetric titrations. The reaction enthalpy gives noevidence of the formation of inclusion or exclusion complexes. ¹H-NMR measurements show that in the case of cucurbit[5]uril and cucurbit[6]uril the organic guest compound is included within the hydrophobic cavity. Decamethylcucurbit[5]uril forms only exclusion complexes with organicamines. This was confirmed by the crystal structure of the decamethylcucurbit[5]uril-1,6-diaminohexane complex.     

A novel supramolecular graft copolymer via cucurbit[8]uril-based complexation and its self-assembly

A novel supramolecular graft copolymer（SGP） composed of viologen-containing copolymer（P（DMA-co-diEV）） as the main chain and Np ended PNIPAM（Np-PN1PAm） as the grafts is prepared（DMA:N,N- dimethylacryamide,diEV:ethylviologen dimer,Np:naphthalene,PNIPAM:poly（N-isopropylacrylamide））. The grafting is based on the triple complexation among a host of cucurbit[8]uril（CB[8]）and two guests of diEV and Np,which is characterized by UV-vis spectra and ITC.Temperature sensitive property of PNIPAm moiety allows SGP to self-assemble into non-covalently connected micelle（NCCM） at high temperature. The micelles are sensitive to reducing agents,for example Na₂S₂O₃,which breaks the current inclusion complex pair and induces aggregation.     

Toward a versatile toolbox for cucurbit[n]uril-based supramolecular hydrogel networks through in situ polymerization

The success of exploiting cucurbit[n]uril (CB[n])-based molecular recognition in self-assembled systems has sparked a tremendous interest in polymer and materials chemistry. In this study, polymerization in the presence of host-guest complexes is applied as a modular synthetic approach toward a diverse set of CB[8]-based supramolecular hydrogels with desirable properties, such as mechanical strength, toughness, energy dissipation, self-healing, and shear-thinning. A range of vinyl monomers, including acrylamide-, acrylate-, and imidazolium-based hydrophilic monomers, could be easily incorporated as the polymer backbones, leading to a library of CB[8] hydrogel networks. This versatile strategy explores new horizons for the construction of supramolecular hydrogel networks and materials with emergent properties in wearable and self-healable electronic devices, sensors, and structural biomaterials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3105–3109     

Synthesis and Crystal Structure of Macrocyclic Cavitand Cu-curbit[5]uril and Its Supramolecular Adduct with Cu(II)

Introduction The cucurbit[n]urils (CB[n]s) are a kind of cyclic methylene-linked glycoluril oligomers and possess a characteristic annular shape, with two identical car-bonyl-fringed portals.1-3 As the most common cucurbi-turil, CB[6], has been widely studied in supramolecular chemistry by the groups of Mock4 and Kim.5 Recently, other CB[n] (n=5, 7, 8), the molecular recognition properties of which are different from those of CB[6] itself, have been extensively utilized in molecular rec-og…     

Synthesis and crystal structures of supramolecular compounds of polynuclear aluminum(III) aqua hydroxo complexes with cucurbit[6]uril

Supramolecular compounds of the di-, trideca-, and triacontanuclear aluminum aqua hydroxo complexes, viz., [Al₂(OH)₂(H₂O)₈]⁴⁺, [Al₁₂(AlO₄)(OH)₂₄(H₂O)₁₂]⁷⁺, and [Al₃₀O₈(OH)₅₆(H₂O)₂₆]¹⁸⁺, respectively, with the organic macrocyclic cavitand cucurbit[6]uril (C₃₆H₃₆N₂₄O₁₂) were prepared by evaporation of aqueous solutions of aluminum nitrate and cucurbit[6]uril after the addition of pyridine, ammonia, KOH, or NaOH at pH 3.1–3.8. X-ray diffraction study demonstrated that the aqua hydroxo complexes are linked to the macrocycle through hydrogen bonds between the hydroxo and aqua ligands of the polycations and the portal oxygen atoms of cucurbit[6]uril. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 261—268, February, 2006.     

Metal ion-assisted assembly of one-dimensional polyrotaxanes incorporating cucurbit[6]uril

Three cucurbit[6]uril (CB[6])-based polyrotaxanes [Cu(H₂ C6N4)(CB[6])]Cl₄·12H₂O (1), [Co(H₂ C6N4)(CB[6])]Cl₄·14H₂O (2) and [Ag(C6N4)(CB[6])]NO₃·7H₂O (3) are prepared using N,N′-bis(4-pyridylmethyl)-1,6-hexanediamine (C6N4) threading into CB[6]'s and metal ions' assistance. Single-crystal X-ray diffraction analyses reveal that polyrotaxanes 1, 2 and 3 all have 1D chain structure where 1 and 2 are linear and 3 has two shapes, linear and sawtooth, respectively. The effects of guest molecules, metal and counter ions as well as intermolecular weak interactions on the architectures of polyrotaxanes are discussed.