Hydrogen-bonded Three-Dimensional Networks Encapsulating One-dimensional Covalent Chains: [Cu(3-ampy)(H_2O)_4](SO_4)·(H_2O) (3-ampy = 3-Aminopyridine)

A three-dimensional complex [Cu（3-ampy）（HEO）4]（SO4）·（H2O） （3-ampy = 3-amino- pyridine） has been synthesized. Crystallographic data： C5H16CuN2O9S, Mr = 343.80, triclinic, space group P1, a = 7.675（2）, b = 8.225（3）, c = 10.845（3）A, α= 86.996（4）, β = 76.292（4）, γ= 68.890（4）°, V = 620.0（3）A^3, Z = 2, Dc = 1.841 g/cm^3, F（000） = 354 and μ = 1.971 mm^-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections （I 〉 2a（/））. The structure consists of [Cu（3-ampy）（H2O）4]^2＋ cations, SO4^2- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO4^2- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO4^2- anions to coordinate water extend the 2D framework into a 3D network.

Synthesis and Structural Characterization of a New Hydrogen-bonded Polyrotaxane of [Co(H_2O)_6]_(2+) with 1,1′-(Propane-1,3-diyl)dipyridinium-4-carboxylate

A new double betaine 1,1′-（propane-1,3-diyl）dipyridinium-4-carboxylate L has been synthesized. Reaction of 1, 1′-（propane-1,3-diyl）dipyridinium-4-carboxylate tetrahydrate 1 with Co（ClO4）2-6H2O leads to the formation of a new Co（Ⅱ） coordination compound, namely [Co（H2O）6]-2H2O-2L-2ClO4 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1. monoclinic, space group C2/c, a = 18.945（4）, b = 7.700（2）, c = l 1.888（2）A,β = 101.67（3）°, V = 1698.3（6） A^3, Z = 4, F（000） = 760.0, Dc = 1.402 g/cm^3, the final R = 0.0607 and wR = 0.1607 for 950 observed reflections （1 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 17.982（1）, b = 15.879 （1）, c = 7.0716（5）/A,β= 100.675（1）°, V= 1984.3（3） ,A^3 Z= 4, F（000） = 1010.0, Dc = 1.631 g/cm^3, the final R = 0.0316 and wR = 0.0896 for 3784 observed reflections （1 〉20（I））. Crystal structure analysis indicates that in 1, molecules of L in a ＂V-shaped＂ conformation are linked to chains sustained by O-H…O hydrogen bonds between carboxylate groups and solvent water molecules. The chains are joined by O-H…O and C-H…O hydrogen bonds to further expand into a three-dimensional structure. For 2, molecules of L in a ＂Z-shaped＂ conformation are linked by hydrogen bonds between carboxylate groups and aqua ligands to form a chain of loops running down the b axis. The （2D→2D） polythreading in compound 2 represents the mode of parallel interpenetration of 2D sheets, having polyrotaxane character.

Syntheses and Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)_2Cl]·ClO_4 and [Zn(bipy)_2Cl]·BF_4

Two new transition metal complexes, [Ni（bipy）2Cl]·ClO4 （bipy = 2,2＇-bipyridine） 1 and [Zn（bipy）2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776（1）, b = 12.067（1）, c = 16.146（2）A, β = 93.021（2）o, V = 2031.9（4） A^3, Mr = 505.98, Dc = 1.654 g/cm^3, μ = 1.255 mm^–1, F（000） = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with Ⅰ 〉 2σ（Ⅰ）. For 2, a = 10.758（4）, b = 12.058（4）, c = 16.135（5） A, β = 104.57（1）o, V = 2025.7（12） A^3, Mr = 500.00, Dc = 1.639 g/cm^3, μ = 1.396 mm^–1, F（000） = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen-sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy ···anion···bipy- M hydrogen bonding interactions between the chelating ligands of bipy and anion.

π-π Stacking, Hydrogen Bonding and Magnetic Coupling Mechanism on a Mono-nuclear Cu^Ⅱ Complex

A new mono-nuclear CuII complex [Cu（DPP）（DP）Br]（ClO4）H2O （DPP = 2-（3,5- dimethyl-1H-pyrazol-1-yl）-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole） has been syn- thesized with 2-（3,5-dimethyl-1H-pyrazol-1-yl）-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765（2）, b = 17.044（3）, c = 10.9044（16）, β= 97.112（2）°, V = 2538.5（6）3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F（000） = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.

A New Cadmium(Ⅱ) Coordination Polymer Extended through Hydrogen Bonds and π-π Stacking Interactions: Synthesis and Photoluminescence Property

A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.

Preparation, Structure and Properties of 3D Supramolecular Architecture, on the Basis of Hydrogen Bonds and π-π Stacking Between 2D Layers, with Windmill Building Blocks

A novel three-dimensional（3D） supramolecular architecture, {[Nd（OH-BDC）（OH-HBDC）（H2O）2]·2HaO）n（1） （OH-H2BDC=5-hydroxyisophthalic acid）, which was formed through hydrogen bonds and π-π stacking between two-dimensional（2D） layers, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Windmill building blocks, which consist of two nine-coordinated metal centers and four OH-H2BDC groups are connected through two carboxyl groups, to lead to a one-dimensional infinite inorganic chain（… M--O--C--O--M…） along the [100] direction. An observed intense blue luminescence with an emission band peaked at 390 nm for compound 1 may results from ligand-to-metal charge transfer（LMCT）. Variable-temperature magnetic susceptibility of compound 1 was investigated and the value was deviated from the Curie-Weiss law.

Effect of Pyridinecarboxylic Acid on the Molecular Packing Architectures of Disc-shaped 2,3,6,7,10,11-Hexahydroxytriphenylene with Both Large π System and Hydrogen Bond Sites

Co-crystallization of 2,3,6,7,10,11-hexahydroxytriphenylene(L)with nicotinic acid(3-pyaH)and isonicotinic acid(4-pyaH)offers L·(3-pyaH)·5 H2O(1)and L·2(4-pya H)·5 H2O(2),respectively.In 1,each L links three neighboring L molecules via O-H···O and C-H···O hydrogen bonds,furnishing a 1 D chain.The hydrogen bonding and p-p stacking deriving from 3-pyaH and L extend the chains to a 2D layer.Lattice water molecules are interconnected to 3-pyaH via hydrogen bonds into a 1 D[(3-pya H)×5 H2O]￥chain.While in 2,Hydrogen bonding between L and 4-pyaH produces a 2D net with triangle and parallelogram grids.Water molecules locate in interlayer and grids,and O(1 w)and O(2 w)link 4-pyaH into a 1 D[(4-pyaH)×2 H2O]∞ chain.

Structure of [Co(im)6]SiF6：Short Hydrogen Bonds Involving SiF62- Ions

A new complex C（18）H（24）CoF6N（12）Si has been synthesized by the reaction of cobalt（II） fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. This complex has been characterized by different techniques such as elemental analysis, IR studies, magnetic measurements, electronic absorption measurements and single-crystal X-ray structure determination. The crystals are hexagonal in the R-3 space group, with a = 13.225（6）, b = 13.225（6）, c = 12.517（11） A, and g = 120°. In complex [Co（im）6]SiF6, the cobalt atom is six-coordinated to adopt a regular octahedral geometry and the SiF62-ion acts as the counter anion. The crystal displays a network structure and SiF62- bridging hexagram formation by N-（39）···F-Si interactions between imdazole and SiF62-. SiF62-plays an important role in assembling the supramolecular aggregates.

A Three-dimensional Organic-inorganic Hybrid Material Supported by Decavanadate Clusters and Na-O Chains: Synthesis and Crystal Structure of [Na_6(H_2O)_(16)(dod)_4V_(10)O_(28)]

A new organic-inorganic hybrid material [Na6(H2O)16(dod)2V10O28] (dod = 1,4- diazoniabicyclo[2,2,2]octane-1,4-diacetate) has been synthesized and X-ray single-crystal structural analysis reveals it crystallizes in triclinic, space group P with a = 11.533(7), b = 12.031(7), c = 12.187(4) ? a = 72.47(1), b = 73.16(1), g = 68.21(1)o, C20H64N4Na6O52V10, V = 1467(1) ?, Z = 1, Mr = 1840.1, Dc = 2.083 g/cm3, MoKa, l = 0.71073 ? m = 1.686, F(000) = 924, S = 1.027, the final R = 0.0538 and wR = 0.1272 for 4398 observed reflections. The compound has a three-dimensional frame- work constructed from decavanadate clusters, NaO chains and dod ligands. A variety of OH…O and CH…O hydrogen bonds play an important role in stabilizing the framework.

Synthesis and Crystal Structure of an Infinite 1D Zigzag Chain Compound (dimbH^+)(ClO_4^-) and Its Comparison with (dimb)2H_2O (dimb = 1,3-Di(imidazol-1-ylmethyl)-5-methylbenzene)

A new imidazolium compound, C15H17N4ClO4, was prepared from a flexible bidentate ligand of 1,3-di(imidazol-1-ylmethyl)-5-methylbenzene, and characterized by X-ray analysis. It is of orthorhombic, space group Pnma with a = 8.182(2), b = 12.874(3), c = 15.611(4) ? V = 1644.4(7) 3, Dc = 1.425 g/cm3, Z = 4, Mr = 352.78, m(MoKa) = 0.944 mm-1, F(000) = 736, S = 1.036, the final R = 0.0521 and wR = 0.1187 for 1128 observed reflections (I > 2s(I)). An infinite one-dimensional zigzag chain is formed by NH…N hydrogen bonding interactions between the imidazolium salt cations.

Synthesis and Crystal Structure of a New Chain Coordination Polymer [Cu(inio)_2(H_2O)]_∞(Inio = Isonicotinic Acid N-Oxide)

A new Cu(Ⅱ) coordination polymer [Cu(inio)2(H2O)] (inio = isonicotinic acid N-oxide) with chemical formula C12H10CuN2O7 was prepared and its crystal structure has been determined by X-ray analysis. The complex crystallizes in the monoclinic system, space group C2/c with a = 12.455(3), b = 6.202(1), c = 16.555(3) ? b = 106.776(3), V = 1224.3(4) 3, Z = 4, Mr = 357.76, Dc =1.941 g/cm3, m(MoKa) = 1.827 mm-1, F(000) = 724, R = 0.0601 and wR = 0.1417 for 908 observed reflections (I > 2s(I)). The Cu(Ⅱ) atom is coordinated by an elongated square pyramid geometry. The deprotonated isonicotinic acid N-oxides form a double-bridge between each pair of Cu(Ⅱ) ions in trans form through two oxygen atoms from the carboxyl groups and two other oxygen atoms from the -NO groups, respectively, which leads to an infinite one dimensional chain. The two adjacent elongated Cu(Ⅱ) square pyramidal geometries are arranged in trans form in the same chain. The OH…O hydrogen bonds extend the chain structure into two-dimensional layers.

Hydrogen-Bonding Crosslinked Supramolecular Polymer Materials:From Design Evolution of Side-Chain Hydrogen-Bonding to Applications

Hydrogen bonds(H-bonds)are the most essential non-covalent interactions in nature,playing a crucial role in stabilizing the secondary structures of proteins.Taking inspiration from nature,researchers have developed several multiple H-bonds crosslinked supramolecular polymer materials through the incorporation of H-bond side-chain units into the polymer chains.N-acryloyl glycinamide(NAGA)is a monomer with dual amides in the side group,which facilitates the formation of multiple dense intermolecular H-bonds within poly(N-acryloyl glycinamide)(PNAGA),thereby exhibiting diverse properties dependent on concentration and meeting various requirements across different applications.Moreover,numerous attempts have been undertaken to synthesize diverse NAGA-derived units through meticulous chemical structure regulation and fabricate corresponding H-bonding crosslinked supramolecular polymer materials.Despite this,the systematic clarification of the impact of chemical structures of side moieties on intermolecular associations and material performances remains lacking.The present review will focus on the design principle for synthesizing NAGA-derived H-bond side-chain units and provide an overview of the recent advancements in multiple H-bonds crosslinked PNAGA-derived supramolecular polymer materials,which can be categorized into three groups based on the chemical structure of H-bonds units:(1)monomers with solely cooperative H-bonds;(2)monomers with synergistic H-bonds and other physical interactions;and(3)diol chain extenders with cooperative H-bonds.The significance of subtle structural variations in these NAGA-derived units,enabling the fabrication of hydrogen-bonded supramolecular polymer materials with significantly diverse performances,will be emphasized.Moreover,the extensive applications of multiple H-bonds crosslinked supramolecular polymer materials will be elucidated.

Chain Extender-induced Hydrogen Bonding Organization Determines the Morphology and Properties of Thermoplastic Polycarbonate Polyurethane

Thermoplastic polycarbonate polyurethanes(PCUs) are multiblock copolymers that have been applied for medical devices for long time. Aliphatic diols are common chain extenders(CE) involved in the composition of the hard segments of PCU. However, limited knowledge was discovered about how the chemical structure of CE affects the hydrogen bonding organization within PCUs and their mechanical properties.To investigate this problem, a group of PCUs were synthesized respectively by extending the polymer chain with 1,4-butanediol(BDO),aminoethanol(MEA), ethanediol(EO) as three kinds of chain extenders. Tiny differences in the CE chemical structure results in remarkable variations in phase separation, condensed morphologies, thermal and mechanical properties, which are characterized by Fourier transform infrared spectrometer, atomic force microscopy, small-angle X-ray scattering, differential scanning calorimetry, and tensile tests. The microstructural evolution during unilateral deformation and the different mechanism induced by the different CEs was probed and unveil by in situ wide-and small-angle X-ray diffraction. Symmetry of CE can improve the organization of the hydrogen bonding. The coherence strength of the urethane/urea group also plays a key role by comparing the two PCUs with ethanediol and aminoethanol.

二元羧酸与4,4′-联吡啶氢键缔合组装主链型超分子液晶

合成了 4 ,4′ 二羧酸 1 ,6 二酚氧基正己烷 ,与等摩尔的 4 ,4′ 联吡啶采用缓慢挥发溶剂的方法组装 ,所得复合体系经DSC分析和偏光显微镜观察表明形成了超分子液晶 。

邻位取代基对芳-脂族共聚酰胺热致液晶性能的影响

通过芳香二酰氯邻位取代基和芳香二元胺邻位取代基对所生成的大分子链的酰胺基的空间阻碍作用和脂肪族二胺与芳香族二胺的适宜配合，使大分子链的刚性和大分子链之间由酰胺基团所形成的氢键减弱，从而降低了熔融温度。

乙烯-乙烯醇共聚物的固体核磁共振研究

A series of ethylene\|vinyl alcohol copolymers (EVOH) with different comonomer contents were studied by both solution state and solid\|state high\|resolution 13 C NMR spectroscopy. A new assignment of 13 C CP/MAS spectrum of EVOH was given. It was demonstrated that the triple splitting of the signal of methine carbon of the vinyl alcohol unit in 13 C CP/MAS spectrum is caused by sequence distribution,tacticity and intra and inter molecular hydrogen\|bonding interactions.

乙烯-乙烯醇共聚物氢键相互作用与链结构关系的变温溶液氢谱研究

用变温溶液核磁共振氢谱研究了不同组成的乙烯 -乙烯醇共聚物在二甲亚砜溶液中的氢键相互作用 .结果表明 ,乙烯醇单元中羟基的信号随温度升高而线性地向高场位移 ,且不同的三单元组中羟基信号的位移速率不同 。

双Sine-Gordon势氢键分子链中孤子的运动

双Ｓｉｎｅ－Ｇｏｒｄｏｎ势氢键分子链模型可以同时描述离子型缺陷孤子和取向型缺陷孤子的协同运动．在此模型的基础上，利用能量分析方法研究这两类孤子在外场中的运动，并计算出它们的迁移率。

N-酰化改性胺扩链剂合成聚脲弹性体的研究

采用N-酰化方法对扩链剂己二胺进行改性。以己二胺、冰乙酸为原料,磷酸为催化剂合成了新型位阻型扩链剂二乙酰己二胺。将扩链剂与4,4′-二苯甲烷二异氰酸酯(MDI)反应,制备了芳香族新型聚脲。结果表明,由二乙酰己二胺合成聚脲的凝胶时间大大延长,同时软段和硬段的相容性较好,扩链的聚脲热稳定性不变,并显示出较高力学性能。

配位聚合物Ni(2,6-DPC)_2Ni(H_2O)_5·2H_2O的水热合成与表征

在水溶剂中通过2,6-吡啶二羧酸和NiCl2.6H2O反应生成三维配位聚合物Ni(2,6-DPC)2Ni(H2O)5.2H2O(DPC=2,6吡啶二羧酸)1。对其进行元素分析、红外光谱分析、热重量分析和单晶X射线衍射测定。该配合物属P2(1)/c。晶胞参数a=8.3261(17),b=27.227(5),c=9.6556(19),β=98.67(3)°,V=2163.9(7)3,Z=7,F(000)=1248,R=0.0618,wR2=0.1721。该配位聚合物中镍配位有两种情况:Ni(1)与6个氧原子配位,有5个是与水分子中的氧配位另外一个是与Ni(2)相连的pdc2-的羧基氧。Ni(2)与全部来自pdc2-的四个羧基氧和两个氮原子配位。未配位的羧基氧和另一单元的配位水之间存在氢键,因此,这个结构集团相连接形成无限的一维链。此外,通过氢键的相互作用结构扩展到二维结构。最终,聚合物在氢键和π-π键作用下拓展为三维网状结构。