Intermolecular Interactions in Self-Assembly Process of Sodium Dodecyl Sulfate by Vertically Polarized Raman Spectra

Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate (SDS) in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.     

Synthesis,Crystal Structure,and Luminescence of a Three-Dimensional Supramolecular Compound Based on a Dinuclear Tin Cluster

A three-dimensional (3D) supramolecular compound, [(phen)LSnS]₂·(H₂O)₂ (phen = 1,10-phenanthroline, L = mercaptoacetic acid), has been synthesized and the crystal structure was determined by a single crystal X-ray diffraction study. 1 is triclinic, space group P-1 with a = 6.695(1) Å, b = 10.929(2) Å, c = 12.117(2) Å, α = 114.55(3)°, β = 93.53(2)°, γ = 104.06(3)°, and Z = 1. The dinuclear cluster of [(phen)LSnS]₂ and H₂O are linked into a 3D supramolecular framework by a combination of O[sbnd]H…O, C[sbnd]H…O hydrogen bonds and π–π stacking interactions. Its luminescence property is discussed.     

2,5-二乙氧甲酰氨基-1,3,4-噻二唑超分子化合物的合成和晶体结构

报道了一种用1,6-二取代二硫脲在DMF中加热回流直接脱H₂S关环合成2,5-二取代1,3,4-噻二唑类化合物的新方法, 并用此方法合成了2,5-二乙氧甲酰氨基-1,3,4-噻二唑. 用元素分析、核磁共振氢谱、红外光谱进行了表征, 用X射线单晶衍射法确定了其单晶结构. 晶体属单斜晶系, P2₁/c空间群, a＝1.0093(4) nm, b＝0.9035(4) nm, c＝1.2924(6) nm, β＝96.785(9)°, V＝1.1703(9) nm³, Z＝4, D_c＝1.477 g/cm³, F(000)＝544, μ＝0.287 mm^－1. 该化合物通过分子间氢键形成了一种二维网状结构的超分子, 由于分子间的作用力使其分子又沿c轴呈层状堆积.     

Two-Dimensional Supramolecular from the Self-Assembly of Dissymmetrical Oxamidato-Bridged Heterometallic Trinuclear Building Blocks: Synthesis, Crystal Structure, and Magnetic Properties

Two heterometallic trinuclear complexes {[Cu(oxbp)]₂Co(H₂O)₂}1.5DMF0.5H₂O (complex 1) and {[Cu(oxbm)]₂Co(H₂O)₂}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]^– and [Cu(oxbm)]^–[H₃oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H₃oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm^–1 for complex 1 and 2, respectively.     

The Crystal Structure and Intermolecular Interactions in Fenamic Acids–Acridine Complexes

In order to improve pharmaceutical properties of drugs, complexes are synthesized as combinations with other chemical substances. The complexes of fenamic acid and its derivatives, such as mefenamic-, tolfenamic- and flufenamic acid, with acridine were obtained and the X-ray structures were discussed. Formation of the crystals is determined by the presence of the intermolecular O–H^…N hydrogen bond that occur between fenamic acids and acridine. Intermolecular interactions stabilizing the crystals such as π^…π stacking, C–H^…X (X = O, Cl) intermolecular hydrogen bonds as well as C–H^…π and other dispersive interactions were analyzed by theoretical methods: the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) approaches.     

A New Azide-Bridged Three-Dimensional Supramolecular Manganese(II) Compound: Synthesis,Crystal Structure and Magnetic Properties

A three-dimensional supramolecular compound [Mn(N₃)₂(H₂O)₃(hmt)] ₂ , where hmt stands for hexamethylenetetramine, was synthesized and characterized by IR, crystal structure and magnetic susceptibility. The compound [Mn(N₃)₂(H₂O)₃(hmt)] _n , crystallizes in the orthorhombic system, space group P_n 2₁ a, with a = 6.5201(9), b = 9.322(2), c = 22.192(3) Å, β = 90° and Z = 2. The Mn atom is coordinated in an octahedral arrangement by three nitrogen atoms from three azido ions, and three oxygen atoms from three water molecules, respectively. The azide ligand bridges Mn atoms in μ-1,3 fashion, forming a zigzag chain. Hmt connected with the zigzag chain by hydrogen bonds, to form a three-dimensional supramolecular structure. The magnetic susceptibility data show that there is an antiferromagnetic exchange interaction in the title compound. The data were modeled using an infinite chain model leading to J = -4.8 cm^?1.     

基于大环醚和三价卤化铋阴离子的超分子杂化化合物：合成、结构及性质

基于大环自组装和多卤阴离子合成了有机-无机杂化超分子化合物,[（1,4-PMNH₃）·（18-crown-6）]·[（H₃O）·（18-crown-6）]₂·[（H₂O）·（18-crown-6）]·（18-crown-6）·（Bi₂Cl₉）（1）。化合物属正交晶系,Pca2₁空间群,a=2.4830（3）nm,b=1.1618（3）nm,c=3.3161（2）nm,V=9.566（2）nm³。并通过其红外光谱、粉末衍射、热重分析和单晶结构分析对化合物进行了充分表征。在转子定子型的超分子化合物1中,大环超分子阳离子和（Bi₂Cl₉）^3-阴离子交错堆积形成包合物结构。并在室温下对其固体荧光性质进行测试表征。通过DSC对其热稳定性进行了详细分析。     

基于大环醚和三价卤化铋阴离子的超分子杂化化合物:合成、结构及性质(英文)

基于大环自组装和多卤阴离子合成了有机-无机杂化超分子化合物,[(1,4-PMNH3)·(18-crown-6)]·[(H3O)·(18-crown-6)]2·[(H2O)·(18-crown-6)]·(18-crown-6)·(Bi2Cl9)(1)。化合物属正交晶系,Pca21空间群,a=2.483 0(3)nm,b=1.161 8(3)nm,c=3.316 1(2)nm,V=9.566(2)nm3。并通过其红外光谱、粉末衍射、热重分析和单晶结构分析对化合物进行了充分表征。在转子定子型的超分子化合物1中,大环超分子阳离子和(Bi2Cl9)3-阴离子交错堆积形成包合物结构。并在室温下对其固体荧光性质进行测试表征。通过DSC对其热稳定性进行了详细分析。     

Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

A new supramolecular compound (4,4'-bipyH)4[SiW12O40](4,4'-bipy) (4,4'-bipy = 4,4'-bipyridine) was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767(12), b = 21.1879(11), c = 15.6942(8) , β = 97.068(3)°, V = 7351.3(7) 3, C50H44N10O40SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F(000) = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiW12O40]4- anion, one 4,4'-bipy and four protonated (4,4'-bipyH)+ cations. The [SiW12O40]4- anion and protonated 4,4'-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.     

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.     

Synthesis and Structure of a Hydrogen-bonding Assembled Three-dimensional Supramolecular Indium(III) Compound Involving One-dimensional Helices

The title compound [In(H2ip)(pdc)(H2O)] (H3ip = 5-hydroxyisophthalic acid, H2pdc = pyridine-2,6-dicarboxylic acid) has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 13.830(8), b = 6.488(4), c = 17.632(10) , β = 92.510(10)°, C15H10InNO10, Mr = 479.06, V = 1580.6(15) 3, Z = 4, Dc = 2.013 g/cm3, F(000) = 944, μ = 1.557 mm-1, the final R = 0.0413 and wR = 0.0793 for 2950 observed reflections with I > 2σ(I). The In(III) ion is seven-coordinated in a slightly distorted penta-bipyramidal geometry. The mixed ligands connect the In(III) ions into 21 helical chains along the [010] direction, and the hydrogen bonds assemble the chains into a three-dimensional supramolecular network.     

Synthesis,Crystal Structure,and Magnetic Properties of a Quasi-one-dimensional Compound Based on TCNQ

A novel compound, （IBzQI）（TCNQ）2 2 （IBzQ1=1-（4-iodobenzyl）quinolinium and TCNQ = 7,7,8,8-tetracyanoquinodimethane） has been fabricated and X-ray single-crystal structurally analyzed. This compound crystallizes in the triclinic system, space group P1 with a = 8.3540（17）, b = 13.284（3）, c = 16.185（3） А, α= 82.12（3）, β= 75.19（3）, γ= 72.34°, V = 1651.2（6） А^3, Z= 2, C_40H_21IN_9, Mr = 754.56, Dc = 1.518 g/cm^3,μ= 1.015 mm^-1, S = 1.010, F（000） = 754, R = 0.0387 and wR = 0.0948. The structure analysis shows that the anions are stacked into column with tetrads, and there are two types of TCNQ entries （TCNQ-1 and TCNQ^0） in agreement with the IR spectra analysis of the compound. The temperature dependence of the magnetic susceptibility （2-300 K） for 2 exhibits spin gap of singlet-triplet feature, and the best fit gave △/kB = 1523.4 K. In order to understand both magnetic behavior and local charge distribution of [（TCNQ）2]-unit, the molecular orbital calculations and analysis based on extended Hückel method were performed, and the results support the analyses of both crystal structure and IR spectra.     

Self-Assembly of Supramolecular Aggregates Based on Sector- and Cone-Shaped Dendrons and Bolaamphiphiles

Using a number of classes of such sector-shaped macromolecules as derivatives of 2,3,4- and 3,4,5- tri(dodecyloxy)benzenesulfonic acid and dendrimers based on gallic acid as an example, the main stages in the formation of supramolecular ensembles are considered: the formation of individual supramolecular aggregates due to the weak noncovalent interactions of mesogenic groups, and the subsequent ordering within these aggregates, which lowers the free energy of a system. Supramolecular aggregates are in turn organized into two- or three-dimensional supramolecular lattices. It is shown that the shape of the supramolecular aggregates and its change along with temperature are functions of the chemical structure of the mesogenic group (resulting in the controlled design of complex self-organizing systems with a given response to external stimuli).     

Self-Assembly and Crystal Structures of Supramolecular (H2O)38 Water Morphology in a Coordination Complex Crystal Host

Abstract  A mono-nuclear copper (II) complex 1, formulated {[Cu(phen)₂(CO₃)]·7H₂O} has been synthesized and characterized by X-ray diffraction studies, FTIR, and thermogravimetric (TG) analysis. However, there is a self-assembly structure of (H₂O)₃₈ cluster in this complex 1, and it is worth reporting. The adjacent (H₂O)₃₈ clusters connect together resulting in an infinite 2D water layer structure. The water morphology is stable at room temperature, but upon thermal decomposition, the water loss is irreversible. Graphical Abstract  A mono-nuclear copper (II) complex 1, formulated {[Cu(phen)₂(CO₃)].7H₂O} has been synthesized and characterized by X-ray diffraction studies, FTIR, and thermogravimetric (TG) analysis. However, there is a self-assembly structure of (H₂O)₃₈ water cluster in this complex 1, and it is worth reporting. The discrete (H₂O)₃₈ cluster connects together resulting in an infinite 2D water layer structure. The alternate arrangement of the complex 1 and the 2D water layer produce infinite through-channels along a axis direction, and the part moieties of complex 1 are located inside these channels. The water rings are stable at room temperature, and when thermally decomposes the water loss is irreversible. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,Crystal Structure and Non-covalent Interactions Analysis of Novel N-Substituted Thiosemicarbazone

()*￡-1 -(4-Fluorobenzylidene)^l-(4-ethylphenyl)thiosemicarbazone was synthesized via the reaction of 4-(4-ethylphenyl)thiosemicarbazide and 4-fluorobenzaldehyde. The title compound was characterized by FTIR, and 13C NMR, mass spectrometry and elemental analysis techniques. Structural property of the title compound was displayed by the X-ray single crystal diffraction. The title compound crystallized in triclinic space group Pl witli a=0.6494(4) nm,a=0.7971(5) nm, c=1.5492( 10) nm,a=83.690( 11)°,β=84.185(10)。γ=84.348(11)。molecular formula Ci6H16FN3S,Mr=301.39,V=0.7868(9) nm^3, Z=2, Dc=1.272 g/cm……3,^000)=316,“=0.213 mm-1, 5=1.02, 7?=O.O513, and cw7[Z>2o(Z)]=0.1662. The intennolecular interactions in the crystal structure were explained using the Hirshfeld surface and their associated two-dimensional fingerprint plots. The title compound showed C-H-S(l-x,-y,-z) and NH(1-y,-z) intermolecular interactions, and formed the supramolecular self-assemblies through R2^2(12) and R2^2(8) ring motifs. Shape index and curvediiess were performed to further understand some unique weak interactions, for instance, the weakπ…π stacking contacts in molecular structure witli difierent characteristic regions. Besides, the reduced density gradient(RDG) function provided a real-space function for discussing non-covalent interactions within molecule, such as hydrogen bonds, weak van der Waals interactions and attractive or repulsive effects.     

二咪唑基苯及硫酸根构筑的钴配位聚合物的合成、晶体结构和磁性质

由溶剂热法合成了钴化合物[Co(dib)(SO4)](1)(dib=1,4-二咪唑基苯),并对其进行了元素分析、IR及X-射线衍射法表征。晶体结构表明:配合物1属于单斜晶系,C2/c空间群。配合物1是由桥联配体1,4-二咪唑基苯连接成二维层状结构,该二维层被硫酸根离子拓展成三维层柱状结构。配合物1的磁性测试研究表明它具有弱反铁磁性。     

Copper(II) Supramolecular Complex: Synthesis,Crystal Structure,and Electrochemical Property

A novel complex {Cu(Bobb)₂](pic)₂}₂ [pic = picrate anion, Bobb = 1,3‐bis(1‐benzylbenzimidazol‐2‐yl)‐2‐oxopropane] was synthesized and characterized by means of elemental analyses and electrical conductivity. The crystal structure of the copper complex has been determined by single‐crystal X‐ray diffraction. A study of the electrochemistry of the title compound was carried out by using cyclic voltammetry. It revealed that the copper complex exhibits a quasi‐reversible redox process. The X‐ray structure of the above complex shows that the unit cell consists of two centrosymmetric, crystallographically independent molecules, in which the copper(II) ions have the same coordination environment and should be described as distorted octahedron. The complex is formed of { ··· Cu(2) ··· Cu(1) ··· Cu(1) ··· }_∞ supramolecular configuration by π ··· π stacking interactions between the benzimidazole rings. The complex was also identified by IR and electronic spectroscopy.     

Conjugate Fluorescent Compound Based on Pyrene-imidazole: Design,Synthesis, Crystal Structure and Fluorescence Property

Pyrenes are an important group of polycyclic aromatic hydrocarbons(PAHs). In order to expand the diversity of conjugate compounds based on pyrene, two new isomeric compounds anti-PyDTPAI and syn-PyDTPAI containing pyrene, imidazole and triphenylamine are synthesized via a one-pot cyclization reaction and characterized. The anti-PyDTPAI is characterized by single-crystal X-ray diffraction which crystallizes in monoclinic, space group P2_1/n with a = 10.132(4), b = 14.997(7), c = 18.968(9) ?, β = 95.543(19)o, V = 2869(2) ?~3, Z = 2, F(000) = 1092, Dc = 1.196 Mg/m~3, Mr = 1033.28 and μ(Mo Kα) = 0.070 mm~(-1). The presence of intermolecular C–H···π interactions results in the stability of the compound. The crystal structure shows a centrosymmetric, coplanar configuration towards pyrene-imidazole segment and a slip-stacked packing mode across the longer molecular axis which is similar to the J-type aggregation. The investigation of UV-vis absorption and fluorescence in solution indicates a strong blue emission under the ultraviolet light excitation. The two isomers also display high thermal stability which is proved by differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA). Additionally, the molecular structure and HOMO and LUMO levels are calculated by density functional theory(DFT) at the B3 LYP/6-31 G(d) level.     

Crystal Structures of the Lanthanum(III), Europium(III), and Terbium(III) Cryptates of Tris(bipyridine) Macrobicyclic Ligands

The crystal structures of the La^III, Eu^III, and Tb^III complexes of macrobicyclic [bpy.bpy.bpy] ligands, [La³⁺ ? 1 ]3 Cl^? ( = 3- La), [Tb³⁺ ? 1 ]3 Cl^? ( = 3- Tb), and [Eu³⁺ ? 2 ]3 C1^? ( = 3- Eu), have been determined. They confirm the cryptate nature of these species, the cations being bound to the eight N-sites of the ligand. The macrobicycle presents two open faces, thus allowing additional coordination of two species, Cl^? ions or H₂O molecules, to the bound cations. These data provide structural support for the photophysical studies of the luminescent properties of the Eu^III and Tb^III cryptates, which indicated residual coordination of H₂O molecules.