Influences of Structure Disorder and Temperature on Properties of Proton Conductivity in Hydrogen-Bond Molecular Systems

The dynamic properties of proton conductivity along hydrogen-bonded molecular systems, for example, ice crystal, with structure disorder or damping and finite temperatures exposed in an externally applied electric-field have been numerically studied by Runge-Kutta way in our soliton model. The results obtained show that the proton-soliton is very robust against the structure disorder including the fluctuation of the force constant and disorder in the sequence of masses and thermal perturbation and damping of medium, the velocity of its conductivity increases with increasing of the externally applied electric-field and decreasing of the damping coefficient of medium, but the proton-soliton disperses for quite great fluctuation of the ＂force constant and damping coefficient. In the numerical simulation we find that the proton-soliton in our model is thermally stable in a large region of temperature of T ≤ 273 K under influences of damping and externally applied electric-field in ice crvstal. This shows that our model is available and appropriate to ice.

Drag reduction and shear resistance properties of ionomer and hydrogen bond systems based on lauryl methacrylate

Based on molecular dynamics simulation results, a lauryl methacrylate polymer with drag reduction and shear resistance properties was designed, and synthesized by emulsion polymerization using 2-vinyl pyridine and methyl methacrylate as the polar polymerization monomer. After ionization of lauryl methacrylate polymer, an ion-dipole interaction based drag reduction agent （DRA） was obtained. The existence of ion-dipole interaction was proven through characterization of the drag-reducing agent from its infrared （IR） spectrum. The pilot-scale reaction yield of the DRA under optimum conditions was investigated, and the drag reduction and shear resistance properties were measured. The results show that： l） The ion-dipole or hydrogen bonding interaction can form ladder-shaped chains, therefore the synthesized DRA has shear resistance properties; 2） The larger the molecular weight （MW） and more concentrated the distribution of MW, the better the drag reduction efficiency and the performance of the ionomer system was superior to that of the hydrogen bonding system; 3） With increasing shear frequency, the drag-reduction rates of both the DRAs decreased, and the drag reduction rate of the ionomer system decreased more slowly than of the corresponding hydrogen bonding system. From the point of view of drag reduction rate and shear resistance property, the ionomer system is more promising than the hydrogen bonding system

Facile synthesis and characterization of novel thermo-chromism cholesteryl-containing hydrogen-bonded liquid crystals

Two series of novel cholesteryl-containing H-bonded liquid crystals were prepared through facile self-assembly between cholesteryl isonicotinate （proton acceptor） exhibiting a monotropic cholesteric phase, and the 4-alkoxy-benzoic acid or 4-alkoxy cinnamic acid （proton donor）. It was found that the increase of the conjugate length as well as the terminal length can contribute to enhance the interaction of molecules and thus significantly influenced the thermal behaviors of H-bonded LCs. The cholesteric reflection spectra of the induced mesogenic complexes were located in the visible region with the color tuneable thermo-sensitivity, which could be used for display application.

Synthesis, Crystal Structure and Photoluminescent Property of a 3D Hydrogen-bonded Supramolecular Compound with Large Channels

The title compound, [Pd（2,2′-bipy）2]（Haadip）2·4H2O, was synthesized via the hydrothermal reaction of PdCl2 with 5-aminodiacetic isophthalic acid （H4adip） in an acetic acid water solution. It was characterized by elemental analysis and infrared spectrum. Crystal data for C44H44N6O20Pd： monoclinic, space group P21/n, a = 11.0674（2）, b = 9.9716（2）, c= 20.5770（3）A, β = 92.7300（3）°, V = 2268.29（7）A^3, Z = 2, Mr = 1083.25, Dc = 1.586 g/cm^3, F（000） = 1112,μ = 0.499 mm^-1, 2（MoKa） = 0.71073 A, T = 293（2） K, 2θmax = 51.38°, GOOF = 1.067, R = 0.0268 and wR = 0.0710 for 3770 reflections with 1 〉 2σ（I）. X-ray diffraction studies reveal that the title compound has an interesting 3D microporous architecture via hydrogen bonds with the cations located inside the channel.

A Novel Porphyrin-based Hydrogen-bonded Organic Framework

A novel hydrogen-bonded organic framework, HOF-TCPP(HOF = hydrogen bonded organic framework, TCPP = tetrakis(4-carboxyphenyl) porphyrin), has been synthesized via solvothermal reaction in ethylene glycol. Crystal structure was well determined by single-crystal X-ray diffraction and powder X-ray diffraction(PXRD). Topological analysis reveals that HOF-TCPP exhibits sql 2D layer and features 2D → 3D polycatenation. Fluorescence investigation shows that HOF-TCPP displays much higher photoluminescence(PL) intensity than the amorphous ligands TCPP, which can be ascribed to the crystalline structure and hydrogen bonds existing in the structure.

Synthesis and Crystal Structure of Co(DMSO)_2(H_2O)_2(SCN)_2 with One-dimensional Hydrogen-bonded Structure (DMSO = Dimethylsulfoxide)

The title complex Co（DMSO）2（H2O）2（SCN）2 has been prepared and structurally characterized. It crystallizes in monoclinic, space group P21/n with a= 5.1981（9）, b = 11.944（2）, c = 12.646（2） A,β = 98.686（2）°, V = 776.2（2） A^3, C6H16CoN2O4S4, Mr = 367.38, Z = 2, De = 1.572 g/cm^3, F（000） = 378 and μ（MoKa） = 1.646 mm^-1. The structure was refined to R= 0.0232 and wR = 0.0645 for 1241 observed reflections with I 〉 2σ（I）. In the title complex, each Co（II） atom is octahedrally coordinated by four O atoms from two DMSO ligands and two water molecules as well as two N atoms from SCN^- ions. The title molecules are connected to each other through intermolecular hydrogen bonds to form a 1-D structure extended by eight-membered Co2O4H2 rings.

Study on UV, IR and NMR Spectra of Double Hydrogen-bonded Complexes

AM 1, PM3 and DPT methods were used to study on the hydrogen-bonded dimer of melamine and [ 1,3] dioxane-2,4,6-trione. The electronic spectra, IR and NMR spectra of some complexes were calculated with INDO/SCI, AM 1 and B3LYP/6-31G（d） methods, respectively. It is demonstrated that the negative stability energy is responsible for the formation of the complexes. Stabilization energies of these complexes were altered among the variations of electric property and steric effects of the monomers. HOMO-LUMO energy gaps were shrunk and the blue-shift of absorptions in the electronic spectra occurred. The vibrations of N-H bonds and chemical shifts of the protons changed with the formation of hydrogen bonds.

Solvothermal Synthesis and Structure Characterization of a 3D Hydrogen-bonded Copper Compound [Cu(H_2dhpmc)_2]·2H_2O

The solvothermal reaction of H3dhpmc (H3dhpmc = 2, 4-dihydroxypyrimidine- 5-carboxylic acid), CuCl2稨2O and NaVO3 results in the formation of a discrete mononuclear Cu(Ⅱ) complex [Cu(H2dhpmc)2]?H2O. It crystallizes in monoclinic system, space group P21/c with a = 5.0497(9), b = 10.0196(6), c = 13.715(2) ? b = 96.237(1)? V = 689.8(2) 3, Z = 2, Dc = 1.973 g/cm3, ?= 1.654 mm-1, F(000) = 414, R = 0.0736 and wR = 0.1351. Each Cu(Ⅱ) is coordinated to four oxygen atoms of two 2, 4-dihydroxypyrimidine-5-carboxylic acid ligands in the equatorial position and two oxygen atoms of two water molecules in the axial position to form an axially elongated octahedral geometry. The title complex is further linked into a three-dimensional structure through the weak interactions of hydrogen bonds between the oxygen atoms and the nitrogen atoms.

Synthesis and Hydrogen-bonded Interpenetrating Grid Structure of 5,5'-Bis[4-(2-hydroxyethyl)phenyl]diazo-dipyrromethane

A new 5,5＇-bisdiazo-dipyrromethane compound 3 has been synthesized and cha- racterized. The crystal of 3 is of orthorhombic, space group Iba2 with a = 19.1914（17）, b = 9.8396（8）, c = 13.7643（12） A, V= 2599.2（4） A3, Z = 4, C29H34N602, Mr = 498.62, Dc = 1.274 g/cm3, F（000） = 1064, μ（MoKa） = 0.083 mm-1, the final R = 0.0302 and wR = 0.0786 for 6361 observed reflections with I 〉 2σ（/）, and R = 0.0320 and wR = 0.08006 for all data. It reveals that the molecules of compound 3 assemble into grid structures through a R22（7） type hydrogen bonding motif between azopyrrole and hydroxyl group. The grids interpenetrate each other with the assistance of C-H...π interaction.

Structures and Hydrogen Bonding Interactions in Urea-water System Studied by All-atom MD Simulation and Chemical Shifts in NMR Spectrum

The interactions and structures of the urea-water system are studied by an all-atom molecular dynamics （MD） simulation. The hydrogen-bonding network and the radial distribution functions are adopted in MD simulations. The structures of urea-water mixtures can be classified into different regions from the analysis of the hydrogen-bonding network. The urea molecule shows the certain tendency to the self-aggregate with the mole fraction of urea increasing. Moreover, the results of the MD simulations are also compare with the chemical shifts and viscosities of the urea aqueous solutions, and the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data such as chemical shifts of the hydrogen atom and viscosity.

Primary Organicamine Templated Indium Iodate (H_2en)KIn(IO_3)_6·2(H_2O) with Hydrogen-bonded Helices

The first primary organicamine templated indium iodate with the formula （H2en）KIn（IO3）6-2（H2O） was hydrothermally synthesized via reaction at 100 ℃ for 7 d and characterized by single-crystal X-ray diffraction and thermal analysis. The compound crystallized in a triclinic system with space group P1, a=0.69803（14） nm, b=0.70863（14） nm, c=1.2091（2） nm, a=76.417（4）°,β=79.953（4）°, γ=72.206（3）°, V=0.55012（19） nm3. Structure determination indicates that it is made up of zero-dimensional units each of which consists of [In（IO3）6]3 anion, potassium, water and ethylenediamine cation. The most striking feature of the compound is that it possesses helical hydrogen bonds formed by organic amine template, water molecules and inorganic network.

Density Functional Calculations on a Double Hydrogen-bonded Dimer

Density functional theory (DFT) calculations on a double hydrogen-bonded dimer of o-hydroxybenzoic acid were carried out at the B3LYP/6-31G* level. The optimized geometry of the dimer closely resembles that of the crystal. The calculated results show that the total energy of the dimer is much lower than the sum energies of the two monomers, and the average strength of the double hydrogen bonds is about 38.37 kJ/mol. In order to probe the origin of the interactions in the dimer, natural bond orbital analyses were performed. The thermodynamic properties of the title compound at different temperatures have also been calculated on the basis of vibrational analyses and ?GT, the change of Gibbs free energy for the aggregation from monomer to the dimmer, is 26.47 kJ/mol at 298.15 K and 0.1 MPa, implying the spontaneous process of forming the dimer. The correlation graphics of S0m, H0m and temperatures is depicted.

Hydrogen-bonded Supramolecular Rosette Ribbon Constructed from Melamine with Isophthalic Acid

The new complex of melamine （MA） with isophthalic acid （H2IA）, [（HMA^＋）- （HIA^-）]·2H2O, has been prepared and its structure was characterized by X-ray crystallography. The crystal is of triclinic, space group P^-1 with a = 7.0228（6）, b = 9.1706（8）, c = 12.170（1） A, α = 95.337（2）, β = 105.247（2）, γ = 97.813（2）^o, V = 742.3（1） A ^3, Mr= 328.30, Z = 2, Dc = 1.469 g/cm^3, ;λ = 0.71073 A,μ（MoKa） = 0.121 mm^-1 and F（000） = 344. The structure was refined to R = 0.0389 and wR = 0.1093 for 2513 observed reflections with I 〉 2σ（I）. Melamine dimer and isophthalic acid anion are interlinked by N-H…N and N-H…O hydrogen bonds, resulting in a 1D rosette ribbon in which water molecules and amino groups are self-assembled into quasihexagonal patterns.

Synthesis and Characterization of a Novel Hydrogen-Bonded Three-dimensional Porous Co(II) Compound

A hydrogen-bonded three-dimensional cobalt(II) compound, {[Co(2,2?-bipy)- (Hbtc)(H2O)3]3H2O}n 1 (H3btc = 1,3,5-benzenetricarboxylic acid, 2,2?-bipy = 2,2?-bipyridine), has been synthesized and characterized by single-crystal X-ray diffraction analysis, IR and TGA. Compound 1 crystallizes in monoclinic, space groups P21/n, C19H36CoN2O12, Mr = 543.43, a = 7.6930(2), b = 19.3715(6), c = 15.9408(5) , = 95.8750(10)o, V = 2363.10(12) 3, Z = 4, Dc = 1.527 g/cm3, = 0.792 mm1, F(000) = 1148, R = 0.0489 and wR = 0.1437 for 4085 reflections. The Co(II) atom is coordinated by an oxygen atom of monodentate Hbtc2, two nitrogen atoms of 2,2?-bipy and three water molecules into a slightly distorted octahedral geometry. The inter- molecular hydrogen bonding interactions among the adjacent [Co(2,2?-bipy)(Hbtc)(H2O)3] extend the compound into a three-dimensional porous supramolecular framework. The uncoordinated water molecules act as space-fillers and consolidate the whole architecture through the hydrogen bonding interactions.

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.

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

New hydrogen bonded supramolecular hydrogels were formed through simultaneously gelating two isomeric building units, 4-oxo-4-（2-pyridinylamino）butanoic acid （G1） and 4-oxo-4-（3-pyridinylamino）butanoic acid （G2） at various molar ratios in water.

Synthesis and Extended 3D Hydrogen-bonded Structure of Complex Tris(violurato-N,O) Cobalt(III) Hexahydrate

The cobalt（Ⅲ） violurato complex （[Co（C4H2N3O4）3]·6H2O, Mr = 635.28） has been prepared and structurally characterized. The crystal is of monoclinic, space group P2 1/n with a = 10.176（1）, b = 11.8010（9）, c = 19.706（2） A°, β= 97.382（3）°, V= 2346.9（4）A°^3, Z = 4, Dc= 1.798 g/cm^3, F（000） = 1296, μ = 0.839 mm^-1, R = 0.0482 and wR = 0.1357. The Co atom in the title compound is six- coordinated by three carbonyl O atoms and three oximido N atoms of three violurato ligands, forming an octahedral coordination geometry. The neighboring molecules are connected together by hydrogen bonds of N-H…O, O-H…O and O-H…N, forming an extended three-dimensional supra- molecular architecture.

Synthesis and Crystal Structure of a 3-D Hydrogen-bonded Supramolecular Decavanadate Compound [Habo]_6[V_(10)O_(28)]·2C_3H_7OH·2H_2O

A new inorganic-organic hybrid supramolecular compound [Habo]6[V10O28]·2C3H7OH·2H2O 1 （abo = R（-）-2-amino-1-butanol） has been synthesized from VO2^＋ in organic solvents and its crystal structure was reported as follows： monoclinic, space group P21/n, a = 11.419（9）, b = 16.811（16）, c = 15.521（12） A, β= 102.98（2）°, V= 2903（4） A^3, Z = 4, C15H46N3O19V5, Mr = 827.25, Dc = 1.893 g/cm^3, 2（MoKα） = 0.71073 A, μ = 1.636 mm^-1, F（000） = 1696, the final R = 0.0696 and wR = 0.1361 for 4641 observed reflections with I 〉 2σ（I）. The compound is based on decavanadate clusters [V10O28]^6-. The hydrogen bonding interactions among Habo^＋ cations, solvents and decavanadate clusters extend 1 into a three-dimensional supramolecular architecture.

A New Series of Charge-assisted Hydrogen-bonded Host Frameworks Based on [Co(en)_3]^(3+)and Dicarboxylates

A new series of metal complex carboxylates（MCC）made of [Co（en）3]3＋（MC）and either 2,6-naphthalenedicarboxylic（NDC）or 4,4-biphenyldicarboxylic（BPDC）were synthesized and structurally characterized.The four new compounds have a general formula（MC）2（C）3·n（guest）with the guests of dimethylformamide（DMF）and dimethyl sulfoxide（DMSO）and water.All the structures represent a pillared-layer type,where the layer consists of MC cations,carboxylate anions or water molecules via a large number of hydrogen bonds.The layers are pillared by the organic residues of NDC or BPDC,resulting in the inclusion cavities where the guest molecules reside.Although their topological structures are similar,they crystallize in different crystal structures due to the rearrangement of pillars and hydrogen-bonded layers.

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.