One-dimensional Coordination Polymers Assembled into Two Supramolecular Frameworks with High Stability

The dual ligand system of V-shaped 5-(4-carboxy-2-nitrophenoxy)-isophthalic acid(Hcn-H2ipa) and dipyridy-type molecules produces two new coordination polymers: {[Ni(cn-Hipa)(bpa)(H2O)3]·1.5H2O}n 1 and {[Cu(Hcn-ipa)(ppe)2]}n 2(bpa = 1,2-bis(4-pyridyl)ethane, and ppe = trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene). Two complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, and thermogravimetric analysis(TGA). Complex 1 is of monoclinic system, space group C2 with a = 25.936(3), b = 7.6100(10), c = 16.558(2), β = 105.9470(10)°, V = 3142.4(7) ?3, Dc = 1.415 g/cm3, Mr = 669.23, Z = 4, F(000) = 1388, μ = 0.687 mm-1, the final R = 0.0397 and w R = 0.0967 for 12070 observed reflections with I 2σ(I). Complex 2 belongs to the triclinic system, space group P1 with a = 10.165(5), b = 14.946(7), c = 15.506(11) ?, α = 106.461(7), β = 102.454(8), γ = 107.861(5)°, V = 2029(2) ?3, Dc = 1.266 g/cm3, Mr = 773.20, Z = 2, F(000) = 794, μ = 0.595 mm-1, the final R = 0.0538 and w R = 0.1378 for 15488 observed reflections with I 2σ(I). Two complexes show that the 1D polymeric chains are cohered together by extensive H-bonds to complete stable supramolecular microporous frameworks.     

Two Orthogonal Halogen-Bonding Interactions Directed 2D Crystalline Supramolecular J-Dimer Lamellae

Dye assemblies exhibit fascinating properties and performances, both of which depend critically on the mutual packing arrangement of dyes and on the supramolecular architecture. Herein, we engineered, for the first time, an intriguing chlorosome-mimetic 2D crystalline J-dimer lamellar structure based on halogenated dyes in aqueous media by employing two distinct orthogonal halogen-bonding (XB) interactions. As the only building motif, antiparallel J-dimer was formed and stabilized by single π-stacking and dual halogen⋅⋅⋅π interactions. With two substituted halogen atoms acting as XB donors and the other two acting as acceptors, the constituent J-dimer units were linked by quadruple highly-directional halogen⋅⋅⋅halogen interactions in a staggered manner, resulting in unique 2D lamellar dye assemblies. This work champions and advances halogen-bonding as a remarkably potent tool for engineering dye aggregates with a controlled molecular packing arrangement and supramolecular architecture.     

Two Three-dimensional Supramolecular Polymer Built from Mixed N-Donor and Carboxylate Ligands

Two new complexes, [Mn(L)(mmbda)(H_2O)](1) and [Co(L)(btc)(H_2O)]·H_2O(2), were synthesized by reacting the corresponding metal(Ⅱ) salts with rigid ligand 1,4-di(1Himidazol-4-yl)benzene(L) and two different carboxylic acids of 5-methylisophthalic acid(H_2mmbda) and 1,2,4-benzenetricarboxylic acid(H_3btc), respectively. The structures of the complexes were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in triclinic, space group P1 with a = 6.9436(4), b = 9.7306(6), c = 15.5302(10) ?, α = 73.7430(10), β = 85.1010(10), γ = 70.0360(10)o, V = 946.75(10) ?~3, Z = 2, C_(21)H_(20)N_4O_5 Mn, M_r = 463.33, D_c = 1.618 g/cm~3, μ = 0.742-1, S = 1.002, F(000) = 474, the final R = 0.0285 and wR = 0.0600 for 4328 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group P2_1/n with a = 12.5216(12), b = 7.3312(8), c = 22.510(2) ?, β = 93.104(2)o, V = 2063.3(4) ?~3, Z = 4, C_(21)H_(18)N_4O_8Co, M_r = 513.31, D_c = 1.646 g/cm~3, μ = 0.892~(-1) mm, S = 1.096, F(000) = 1044, the final R = 0.0673 and wR = 0.1780 for 3594 observed reflections(I 2σ(I)). Both of complexes are one-dimensional(1D) chain structures and rich hydrogen bonds extend such 1D chains to form three-dimensional(3D) supramolecular polymers.     

New Hydrogen Bonded Supramolecular Hydrogels Formed through Gelating Two Isomeric Building Units Simultaneously

Supramolecular hydrogels formed from small organic molecules (gelators) in water have gained much attention these years due to their scientific interests and potential applications1. However, most of the gelators possesses rather complicated structures an…     

Structures,Properties and Theoretical Studies on Two Viologen/Iodoargentate Supramolecular Hybrids

Two iodoargentate hybrids templated by viologen or viologen-like cations, i.e. [MV(Ag_2I_4)]n(1) and [MBYP(AgI 2)]n(2),(MV~(2+) = methyl viologen, MBYP+ = 1-methyl-2,2?-bipyridine) have been synthesized in polar organic solvents.(Ag_2I_4)2-n and(Ag I2)2- n chains in both compounds were constructed from edge-sharing of normal and distorted Ag I4 tetrahedra, and a 2-D supramolecular layer based on C–H···I hydrogen bond was observed in 1. The band gaps of 1.54 and 2.67 e V indicated their semiconductor nature. Their band gap difference was led by different hydrogen bond donors in MV~(2+) and MBYP+, which result in more diffused p-π* antibonding orbitals in MV~(2+).     

基于2,3,5,6-四氟对苯二甲酸构筑的两个超分子网络结构的合成、结构和荧光性质(英文)

在水热条件下合成了基于四氟对苯二甲酸的2个二维微孔配位聚合物{[Cd2(IP)2(tfBDC)2(H2O)2]·H2O}n(1)和{[Mn2(IP)2(tfBDC)2(H2O)2]·H2O}n(2)(tfBDC=2,3,5,6-四氟对苯二甲酸,IP=1-H-咪唑[4,5-f][1,10]-菲咯啉)。二维层状结构是44-网状结构,三维超分子结构是由氢键连接相邻的二维层状结构而形成的。2个配位聚合物均用元素分析、热重分析(TGA)、粉末衍射(PXRD)、红外光谱(FT-IR)进行了表征,且对配合物1的荧光性质进行了详细的分析。     

Sensitivity in Supramolecular Architectures of Polyaromatic Salts Containing Two Singly‐Pimerized Bipyridines

Three novel supramolecular arrays of zigzag polyaromatic salts are reported. Both the conformation and disposition of the dications are subjected to various noncovalent interactions. Thus, the presence or absence of the π‐π interacting enclathrated molecules, the efficient packing and the involved hydrogen bonding interactions of anions, as well as the increased hydrophobic property of the dications themselves exert influence.     

基于2，3，5，6-四氟对苯二甲酸构筑的两个超分子网络结构的合成、结构和荧光性质

在水热条件下合成了基于四氟对苯二甲酸的2个二维微孔配位聚合物{[Cd₂（IP）₂（tfBDC）₂（H₂O）₂]·H₂O}_n（1）和{[Mn₂（IP）₂（tfBDC）₂（H₂O）₂]·H₂O}_n（2）（tfBDC=2,3,5,6-四氟对苯二甲酸,IP=1-H-咪唑[4,5-f][1,10]-菲咯啉）。二维层状结构是4⁴-网状结构,三维超分子结构是由氢键连接相邻的二维层状结构而形成的。2个配位聚合物均用元素分析、热重分析（TGA）、粉末衍射（PXRD）、红外光谱（FT-IR）进行了表征,且对配合物1的荧光性质进行了详细的分析。     

Syntheses, Structures and Luminescent Property of Two Supramolecular Complexes Containing N-P-Acetamidobenzenesulfonyl-glycine Acid Ligand

Making use of N-P-acetamidobenzenesulfonyl-glycine acid （abbreviated as abglyH2）,two transitional metal complexes [Zn（abglyH）（phen）2]ClO4·H2O （1） and Co（abglyH）2（bipy）2（H2O）2 （2） （phen = 1,10-phenanthroline,bipy = 4,4＇-bipyridine） have been synthesized under mild conditions and characterized by IR,elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound which is further assembled by intermolecular hydrogen bonds and π-π interaction into a 2-D supramolecular network. Complex 2 is also a monomeric compound and further connected by intermolecular hydrogen bonds to form a 2-D supramolecular network. Fluorescent analysis shows that complex 1 has an emissive maximum at 364 nm in the solution state at room temperature.     

超分子有机框架:具有周期性孔结构的超分子聚合物

本文概述了水相周期性超分子有机框架(supramolecular organic frameworks,SOFs)的研究进展.首先介绍了水相超分子聚合物和多孔材料研究的背景,然后分别描述了二维单层、三维金刚石型和立方型SOF的构建、结构表征及功能.最后就SOF的未来应用前景做出了分析和展望.     

Supramolecular Polymerizations

Unimers of both natural and synthetic origin self‐assemble into linear, helical, columnar, planar and three‐dimensional structures depending upon the functionality of supramolecular interactions. Recent reports describing the mechanism of formation, properties and possible applications of these systems are critically reviewed. The assembling of one‐dimensional systems produces equilibrium polymers showing a length distribution and a degree of polymerization that may far exceed that of typical condensation polymers. Their growth may occur by a step‐by‐step process akin to polycondensation, and by cooperative processes such as helical growth or growth coupled to liquid crystallinity. Of particular interest are functional systems based on the coupling of a chemical reaction to supramolecular polymerization, and systems based on a covalent polymer hosted within the cavity of a supramolecular one. The assembly of two and three‐dimensional systems occurs through a process akin to crystallization. The supramolecular organization of amphiphiles such as block copolymers is currently well described by the mean‐field theory of unstable modes in homogeneous melts. An alternative, less sophisticated approach considers the growth of specifically designed building blocks. Possible applications are in areas that expand the uses of covalent polymers, electrochemical and photonic devices, ion‐selective channels, separation processes, microengines mimicking the performance of biological systems, storage of sequential information, biocompatible and patterned surfaces, sensors. A classification including additional systems that have been described as supramolecular polymers is presented.     

Supramolecular chemistry

The article discusses molecular recognition and overviews the key concepts -storage and retrieval of chemical information by molecular structures, supramolecular reagents and catalysts, molecular transport, semiochemistry and self assembly. The prospects of controlling supramolecular architecture through engineered molecular recognition and design of ‘programmed systems’ controlled by molecular information are also discussed.     

两个基于4-咪唑羧酸配体超分子配位聚合物的合成、结构和性质

以含4-咪唑和羧酸基团的双功能基团4-咪唑基苯甲酸(HL1)为配体,用水热法合成了2个超分子化合物[Cd(L1)(HL1)I](1)和[Co2(L1)4(H2O)8](2),并进行了元素分析、红外、热重、粉末衍射及X-射线单晶衍射等表征。晶体结构解析结果表明:配合物1属于单斜晶系,P21/c空间群,L1-配体连接Cd( Ⅱ)离子成一维链,这些一维链通过氢键连接成三重贯穿的α-Po结构的超分子聚合物;配合物2不对称结构单元中,存在3种不同的金属Co( Ⅱ)中心单核分子,这些相互独立的分子单元通过丰富的氢键连接成三维的聚合物。同时,对配合物1室温下的固体荧光性质和配合物2对气体的吸附性能进行了研究。     

两个基于4-咪唑羧酸配体超分子配位聚合物的合成、结构和性质

以含4-咪唑和羧酸基团的双功能基团4-咪唑基苯甲酸(HL₁)为配体,用水热法合成了2个超分子化合物[Cd(L₁)(HL₁)I] (1)和[Co₂(L₁)₄(H₂O)₈] (2),并进行了元素分析、红外、热重、粉末衍射及X-射线单晶衍射等表征。晶体结构解析结果表明:配合物1属于单斜晶系,P2₁/c空间群,L₁-配体连接Cd(Ⅱ)离子成一维链,这些一维链通过氢键连接成三重贯穿的α-Po结构的超分子聚合物;配合物2不对称结构单元中,存在3种不同的金属Co(Ⅱ)中心单核分子,这些相互独立的分子单元通过丰富的氢键连接成三维的聚合物。同时,对配合物1室温下的固体荧光性质和配合物2对气体的吸附性能进行了研究。     

通过自分类构筑以两种分立金属有机大环为交联点的超分子聚合物凝胶

通过合理分子设计,合成了分别含有柱芳烃主体基元和氰基客体基元且具有不同尺寸的吡啶给体D1和D2,同时选择120?双铂金属盐A作为受体,从三组分出发,通过"一锅法"配位键导向自组装,自分类得到分别含有3个柱[5]芳烃单元的金属有机大环H和含有3个氰基中性客体的金属有机大环G.随着体系浓度增大,通过柱芳烃共价大环与中性氰基客体之间主客相互作用,逐级自组装形成以2种分立金属有机大环为交联点的新型超分子聚合物.所得到的超分子聚合物通过变浓度核磁氢谱(1H-NMR)、动态光散射(DLS)、二维核磁扩散序谱(DOSY)、扫描电镜(SEM)等进行了表征.有趣的是,进一步增加浓度(9.9 wt%),超分子聚合物转化成超分子聚合物凝胶,并且在温度、中性有机小分子及卤素离子等多重刺激下实现凝胶-溶液的可逆转化.     

Two 3-D Supramolecular Networks Containing Dimeric {Cu2X2} Cluster Units

Abstract  Two new 3-D supramolecular compouds: [Cu₂X₂(Hpyba)₂]_n (X = Br (1), I (2), Hpyba = 4-pyridin-4-yl-benzoic acid) have been hydrothermally synthesized and structurally characterized. Although both compounds exhibit different space groups, they have a similar structure. Each {Cu₂X₂} cluster unit interconnects to form a 1D stair-step chain. The Saturated Hpyba ligands are regularly appended to both sides of main chain, linked via N atoms of ligands. These infinite chains are further linked by H-bonds and π–π interactions to form a 3-D supramolecular network structure. The thermal stability of 1 and 2 was investigated by thermogravimetric measurements. Graphical Abstract  Two new 3-D supramolecular compouds [Cu₂X₂(Hpyba)₂]_n (X = Br(1), I(2), Hpyba = 4-pyridin-4-yl-benzoic acid) have been obtained under hydrothermal conditions. Both compounds exhibit a 1D stair-step chain structure based on the {Cu₂X₂} cluster units. These infinite chains are further linked by H-bonds and π–π interactions into forming a 3-D supramolecular network with two types of channels along different directions.      

Two Supramolecular Nickel(II) Complexes: Syntheses,Crystal Structures and Solvent Effects

Two nickel(II) complexes, namely {[NiL(MeOH)(μ‐OAc)]₂Ni} · 2CH₂Cl₂ · 2MeOH ( 1 ) and {[NiL(EtOH)(μ‐OAc)]₂Ni} · 2EtOH ( 2 ) {H₂L = 5, 5′‐dimethoxy‐2, 2′‐[(ethylene)dioxybis(nitrilomethylidyne)]diphenol}, were synthesized and structurally characterized. Two trinuclear Ni^II complexes are both hexacoordinate around the central Ni^II atoms, showing octahedral coordination arrangements, and each complex comprises three divalent Ni^II atoms, two deprotonated L^2– ligands, in which four μ‐phenoxo oxygen atoms forming two [NiL(X)] (X = MeOH or EtOH) units, and coordinated and non‐coordinated solvent molecules. Complex 1 exhibits a 2D supramolecular network through intermolecular O–H ··· O, C–H ··· O and C–H ··· π interactions, whereas complex 2 forms an infinite 1D chain by intermolecular C–H ··· O hydrogen bonding interactions.