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（英文）

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[ZnCl_4]~(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。     

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。     

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（英文）

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。     

十甲基五元瓜环与几种金属离子配合物的晶体结构

合成了3个十甲基五元瓜环(Me₁₀Q[5])分别与铷离子、铈离子水合物相互作用形成的配合物以及四氯锌根离子存在下形成的单晶体,并测定了其单晶结构。3个配合物均形成以Me₁₀Q[5]为“胶囊体”,水分子为“胶囊”芯材,金属离子或水分子为“胶囊盖”的“分子胶囊”结构,并通过配键或氢键组装形成一维超分子链结构实体。     

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)}·xH₂O (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-NDA^2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA^2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成三维超分子结构。此外,还研究了自组装体1和4的荧光传感性能,结果表明它们都能够作为抗生素诺氟沙星(NFX)的比率型荧光探针。     

碱土金属在Q[5]-CdCl_2体系中配位超分子自组装体的构筑(英文)

通过X射线单晶衍射仪的结构表征技术,研究了碱土金属在五元瓜环-四氯镉酸根体系中的配位超分子自组装体的构筑。晶体结构表明:[CdCl4]2-的存在,能够使得碱土金属与五元瓜环形成分子胶囊。研究结构还发现,在这样的体系即使没有[CdCl4]2-或"蜂巢效应"存在,由于瓜环的外壁作用也能够促使这种结构形成。     

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。     

Coordination of Alkaline Earth Metal Ions in the Inverted Cucurbit[7]uril Supramolecular Assemblies Formed in the Presence of [ZnCl4]2− and [CdCl4]2−

A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water‐soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H⁺ form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE²⁺) in aqueous HCl solutions in the presence of [ZnCl₄]^2? and [CdCl₄]^2? anions as structure‐directing agents. Single‐crystal X‐ray diffraction analysis revealed that both iQ[7]–AE²⁺–[ZnCl₄]^2?–HCl and iQ[7]–AE²⁺–[CdCl₄]^2?–HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl₄]^2? and [CdCl₄]^2? anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE²⁺ coordination polymers through outer‐surface interactions of Q[n]s.     

四个CyB5Q[5]-Ca配合物的晶体结构和在不同阴离子环境下的不同配位状态

在不同阴离子介质中,利用瓜环家族新成员CyB₅Q[5]与钙离子生成了4个CyB₅Q[5]-Ca配合物（1~4）,用X射线单晶衍射确定了它们的结构。晶体结构表明,在Cl^-、[ZnCl₄]^2-、[ZnCl₄]^2-+ClO₄^-和ClO₄^-环境下,分别生成了不同配位类型的配合物。     

Homo- and heterometallic complexes based on polytopic carboxylic acid: synthesis,characterization, and property

Two heterometallic [K₄M₄(HL)₄(H₂O)₁₂] (M=Co (1), Ni (2)) and two homometallic [M₂L(H₂O)₇]?·?2H₂O ((M=Co (3), Ni (4)) (H₄L?=?(2-(bis(carboxymethyl)amino) terephthalic acid) have been synthesized and characterized by elemental analysis, FT-IR spectrum, and single-crystal X-ray diffraction. The isomorphous 1 and 2 contain K⁺ and M²⁺, in which K⁺ were bridged with M²⁺ through μ-HL^3? and μ-H₂O, leading to 2-D layer structures. The isomorphous 3 and 4 show homometallic binuclear complexes with μ-HL^3? as the bridging ligand. Various H-bonds including different H-bond helical chains form, by which 3 and 4 assemble into 3-D supramolecular frameworks. TG analysis indicates that the decomposition temperatures are [K₄M₄(HL)₄(H₂O)₁₂] (1)?>?[M₂L(H₂O)₇]?·?2H₂O (3)?>?H₄L.     

Ionothermal synthesis and characterization of two new heteropolytungstates with 1-ethyl-3-methylimidazolium bromide ionic liquid as solvent

In this article, we have synthesized two new heteropolytungstate-based compounds [EMIM]₄[SiW₁₂O₄₀] (1) and [EMIM]₆[P₂W₁₈O₆₂] · 4H₂O (2) using the ionic liquid (IL) [EMIM]Br (EMIM = 1-ethyl-3-methylimidazolium) as a solvent and characterized them by infrared (IR) and ultraviolet (UV) spectra, thermogravimetric (TG) and elemental analyses, electrochemistry, and single-crystal X-ray analyses. Compound 1 is constructed from one [SiW₁₂O₄₀]^4? and four [EMIM]⁺. In the structure, [SiW₁₂O₄₀]^4? and [EMIM]⁺ are connected by hydrogen bonds with the surface oxygens of the polyoxoanion to form a 3-D supramolecular framework. The heteropolyanion of 2 is a classical Dawson-type structure [P₂W₁₈O₆₂]^6? and connected with six cations through hydrogen bonds. The structures of these two heteropolyanions are consistent with those synthesized by traditional methods, indicating that ionothermal synthesis is an effective method for the preparation of heteropolyoxometalates. The photocatalytic properties of these compounds have also been investigated.     

Template construction of a series of supramolecular coordination polymers via 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium cation

Five cation-induced complexes, (phen-dzp) [ZnBr₃N₃] (1), (phen-dzp) [ZnCl₂Br₂] (2), (phen-dzp) (H₃O)₂ [Fe(CN)₆] (3), (phen-dzp)₂ [Cu₂I₆] (4), and [(phen-dzp)(Ag₂Br₄)] _n (5) [phen-dzp?=?(C₁₅H₁₄N₂)²⁺, 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium], have been synthesized via self-assembly in solution. The crystal structures of 1–3 show that they all crystallize in monoclinic systems with mononuclear structures. Compound 4 is a binuclear coordination polymer. Complex 5 possesses a 2-D supramolecular layer with the organic cation phen-dzp trapped in it; interestingly, each inorganic polymeric planar layer is composed of large, decagon rings formed by sharing four Br^? and four [Ag₂Br₄] quadrilateral units with six adjacent decagon rings. The results provide insights into template effects of synthetic approaches on the construction of supramolecular compounds. The structures of 1–5 have been characterized by elemental analysis, infrared spectra, and single-crystal X-ray crystallography. Solid-state photoluminescence properties of 1–5 have been determined.     

Propane‐1,3‐diaminium tetrachloridozincate(II) 18‐crown‐6 clathrate

The reaction of propane‐1,3‐diamine hydrochloride, 18‐crown‐6 and zinc(II) chloride in methanol solution yields the title complex salt [systematic name: propane‐1,3‐diaminium tetrachloridozincate(II)–1,4,7,10,13,16‐hexaoxacyclooctadecane (1/1)], (C₃H₁₂N₂)[ZnCl₄]·C₁₂H₂₄O₆, with an unusual supramolecular structure. The diprotonated propane‐1,3‐diaminium cation forms an unexpected 1:1 supramolecular rotator–stator complex with the crown ether, viz. [C₃H₁₂N₂(18‐crown‐6)]²⁺, in which one of the –NH₃⁺ substituents nests in the crown and interacts through N—H...O hydrogen bonding. The other –NH₃⁺ group interacts with the [ZnCl₄]²⁻ anion via N—H...Cl hydrogen bonding, forming cation–crown–anion ribbons parallel to [010].