Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH_2]^(2+)·[SbCl_5]^(2-)}_2

A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.

Synthesis and Structural Characterization of a Supramolecular Compound [(C_8H_9NO_2)·HgI_2]_n Constructed from Hg…I and C–H…O Linkage

The title complex [（C8H9NO2）·HgI2]n has been synthesized from the reaction of pyridine-3-ethylformate with mercury iodide in the mixture of DMF and absolute methanol. Its structure was determined by IR, elemental analysis and X-ray single-crystal diffraction analysis. The crystal is of monoclinic system, space group P21/n with a = 4.3397（5）, b = 25.051（3）, c = 12.3719（13）A, β = 92.2130（10）°, CsH9HgI2NO2, Mr = 605.55, V = 1344.0（3）A^3, Z = 4, Dc = 2.993 mg·m^-3, F（000） = 1064, μ = 16.024 mml, the final R = 0.0258 and wR = 0.0504. In the title complex, the center Hg（II） exhibits a four-coordinated distorted tetrahedral geometry. A three-dimensional network arrangement is presented via Hg…I weak interactions among adjacent molecules.

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Novel Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH_2]_2·[BiCl_6]·Cl}

A novel supramolecular compound,{[2-（2-pyridyl）benzimidazoleH2]2·[BiCl6]·Cl},was synthesized by the hydrothermal reaction of o-phenylenediamine and α-pyridinecarboxylic acid with BiCl3 in 6.0 mol·L-1 HCl solution,and characterized by elemental analysis,IR,X-ray single-crystal diffraction and photoluminescence spectroscopy.The crystal （C24H22N6Cl7Bi,Mr= 851.61） belongs to the triclinic system,space group P1 with a =7.2887（18）,b =9.548（2）,c= 12.469（3）,α=85.306（4）,β=82.814（4）,γ=71.349（4）°,Z=1,V=814.9（3）3,Dc=1.735 g/cm3,μ（MoKα）=6.007 mm-1,F（000）=410,R=0.0307 and wR=0.0787.The bismuth ion and six chlorine ions construct a distorted octahedral configuration.The three-dimensional supramolecular network is built from electrostatic attractions,hydrogen bonds and π-π interaction between the BiCl6 anion,Cl anion and [2-（2-pyridyl）benzimidazoleH2] cation.The photoluminescence spectroscopy study shows that the title compound has a blue fluorescent emission at 450 nm in the solid state.

Synthesis,Structure and Electrochemical Property of a Supramolecular Compound(H_2en)_2[Cu(en)_2(H_3O)_2][Mo_8O_(28)]

A supramolecular compound（H2en）2[Cu（en）2（H3O）2][Mo8O28]（en=ethylenediamine） was hydrothermally prepared and confirmed by elemental analysis and TG analysis.Single-crystal X-ray analysis reveals that the crystal crystallizes in the triclinic system,space group P1 with a=9.4635（4）,b=9.8645（5）,c=10.9794（5）A,α=69.2050（10）,β=72.3730（10）,γ=78.4510（10）o,Mr=1559.55,V=908.24（7）A^3,Z=1,Dc=2.851 g/m^3,F（000）=749,μ=3.350 mm^-1,S=1.000,the final R=0.0217 and wR=0.0567.The compound consists of（H2en）^2＋,[Mo8O28]^8-anion and [Cu（en）2（H3O）2]^2＋ cations and constructs a 3D supramolecular structure through hydrogen bonds between the nitrogen atoms from en of [Cu（en）2（H3O）2]^4＋ fragments and the terminal oxygen atoms from the [Mo8O28]^8-polyoxoanions.The electrochemical behavior of this compound has been studied in detail based on a solid bulk modified carbon paste electrode of compound（CPE）.

Synthesis and Structure of a Novel Supramolecular Compound [Co(2,2′-bipy)(H_2O)_4 ][trans-1,4-chdc] and Separation of Isomer of 1,4-Cyclohexanedicarboxylic Acid

A supramolecular compound, [ Co（2,2＇-bipy） （ H2O）4 ] [ trans-1,4-chdc ] （ compound 1 ） （ 2,2＇-bipy = 2,2＇- bipyridine, 1,4-chdcH2 = 1,4-cyclohexanedicarboxylic acid）, was synthesized and characterized by single-crystal Xray diffraction analysis, IR spectrometry, TG analysis, and elemental analyses. Single-crystal X-ray diffraction analysis revealed that [ Co（ 2,2＇-bipy） （ H2O）4 ]^2＋ units and adjacent 1,4-chdc^2- formed a single layer by hydrogen bonding and electrostatic interactions along the ac-plane, and two symmetry-related single layers interacted with each other by hydrogen bonding, resulting in a double layer, which further formed a 3-D structure by π-π stacking. The most attractive structural feature of compound 1 is that 1,4-chdc2- possesses only tram-conformation although there are both c/s- and tram-conformations in the raw material.

Construction of a Ytterbium Supramolecular Compound from 5,5＇-（Buta-diyne- 1,4-diyl）diisophthalic Acid

A novel 3D ytterbium supramolecular compound, [Yb（HBDDC）（H20）4]·2H2O（1）, was synthesized via 5,5＇-（buta-diyne-1,4-diyl）diisophthalic acid ligand（HaBDDC） under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in triclinic system, PT space group with a=0.71372（14） nm, b=1.0566（2） nm, c=1.7969（4） nm, a=101.01（3）°, β=98.15（3）°, γ=99.17（3）° and V=1.2922（4） nm3. Compound 1 exhi- bits a special infinite 1D chain, which stacks parallel each other in an ABAB sequence, leading to the formation of a 3D supramolecular structure owing to the strong π-π interactions between adjacent phenyl ring groups. Moreover, compound 1 manifests excellent luminescent property.

Synthesis and Crystal Structure of a Novel Three-dimensional Supramolecular Compound [(AgI_3)(4-HBPFA)_2(H_2O)]

The supramolecular compound [(AgI3)(4-HBPFA)2(H2O)] (Mr = 1361.11) was synthesized via the reaction of 1,1?-bis[(4-pyridylamino)carbonyl]ferrocene (4-BPFA) with AgI, and structurally characterized by single-crystal X-ray diffraction analysis. Crystal data: monoclinic, space group C2/c, a = 1.6783(3), b = 10.646(2), c = 2.5419(5) ?, β = 93.66(3)o, V = 4532.2(16) ?3, Z = 4, Dc = 1.995 g/cm3, F(000) = 2632 and μ = 3.158 mm-1. The compound consists of (4- HBPFA)+, (AgI3)2- and H2O. In the structure, the adjacent (4-HBPFA)+ are linked by C–H…O and N–H…N hydrogen bonds into 1-D chains which are further linked by C–H…I and N–H…I hydrogen bonds as well as intermolecular π-π stacking interactions to form a 3-D supramolecular compound.

Syntheses, Crystal Structures, Thermal and Fluorescent Properties of Two New Bearing Bi(Ⅲ) Supramolecular Compounds

Two new bearing Bi(Ⅲ) supramolecular compounds [Bi(pydcH)_(3)(Bi(pydcH)(pydcH_(2))(pydc)(Bi(pydcH)(pydcH_(2))(pydc)](1) and {[Bi(pydcH)_(3)]·(H_(2)O)_(5)(Dmap)}_(2)(2) have been successfully synthesized via hydrothermal reaction(pydcH_(2) = 2,6-pyridine dicarboxylate, Dmap = 4-dimethylamiopyridine). They have been structurally determined by single-crystal X-ray analysis, and characterized by fluorescence analysis and thermogravimetric analysis(TG). Both compounds 1 and 2 are of the same triclinic system with different structures. The decomposition mechanisms of compounds 1 and 2 are discussed. Compared to 1, lots of small molecules were possibly removed from compound 2 below 250 ℃. In addition, the photoluminescence properties were also investigated.

Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6·(PhCH_2NC_9H_7)_4]·12H_2O

A novel ionic compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O（C70H80FeN10O12, Mr = 1309.29） has been synthesized and its structure was characterized by I-R, elemental analysis and X-ray diffraction. The compound crystaUizes in triclinic, space group P1, with a = 10.968（7）, b = 11.466（7）, c = 14.077（8）A, α= 87.014（7）, β= 78.124（7）, γ = 72.708（7）°, V = 1654.1（17）A3, Z = 1, Dc = 1.314 g·cm^-3, F（000） = 692, p = 0.298 mm^-1, the final R = 0.0519 and wR = 0.1355. The building unit of the title compound consists of four （PhCH2N＋C9H7） ions, one [Fe（CN）6]4- anion, and a dozen water molecules. According to the structural analysis, [Fe（CN）6]4- ions are linked together by O-H…O and O-H…N hydrogen bonds, while （PhCH2N＋C9HT） and [Fe（CN）6]4- ions interact with each other by electrostatic force to form an ionic compound.

Syntheses and Crystal Structures of Two New Supramolecular Architectures Constructed from the Main Group Metal Chloride and Protonated 2-(3-Pyridyl)benzimidazole

The reactions of SbCl3 and HgCl2 with 2-（3-pyridyl）benzimidazole （PyBIm） in solution acidified with HCl have been investigated. The PyBIm ligands are protonated into 2-（3-pyridinio）benzimidazolium （H2PyBIm） cations and the corresponding metal ions are bonded with chloride atoms into coordination anions, forming two new coordination compounds, namely, （H2PyBIm）（SbCl5） 1 and （H2PyBIm）2（Hg2Cl8） 2. Both compounds were characterized by X-ray crystallography. Crystal data for 1： triclinic, space group P1^- with a = 5.7030（7）, b = 9.0625（11）, c = 16.5929（18） A, α = 91.808（7）°, β = 93.234（6）, γ = 99.216（7）°, C12H11N3SbCl5, Mr = 496.24, V = 844.44（17） A^3, Z = 2, Dc = 1.952 g/cm^3, μ（MoKα） = 2.419 mm^-1, F（000） = 480, the final R = 0.0496 and wR = 0.1382 for 3433 observed reflections （I 〉 2σ（I））. Crystal data for 2： monoclinic, space group P21/c with a = 7.8061（5）, b = 15.8127（9）, c = 12.2435（9） , β = 91.955（4）o, C24H22N6Hg2Cl8, Mr = 1079.26, V = 1510.40（17） 3, Z = 2, Dc = 2.373 g/cm3, μ（MoKα） = 10.889 mm-1, F（000） = 1008, the final R = 0.0293 and wR = 0.0562 for 2854 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that the antimony（III） is five-coordinated, exhibiting a slightly distorted square-pyramidal coordination geometry; while in 2, a dimeric [Hg2Cl8]^4-anion consists of two trigonal bipyramids sharing two common edges. The organic cations and coordination anions are connected into a one-dimensional belt and a two-dimensional sheet through N-H···Cl hydrogen bonding interactions in compounds 1 and 2, respectively; both are further aggregated into 3D frameworks by strong π-π contacts.

A Three-dimensional Supramolecular Complex {[Co(H_2btec)(2,2'-bipy)(H_2O)_3]·H_2O}_n Assembled via Hydrogen Bonding and π-π Stacking Interactions

A new cobalt compound,{[Co（H2btec）（2,2＇-bipy）（H2O）3]·H2O}n （1,H4btec=1,2,4,5-benzenetetracarboxylic acid,2,2＇-bipy=2,2＇-bipyridine）,has been synthesized and charac-terized by single-crystal X-ray diffraction,elemental analysis,IR and X-ray powder diffraction.The crystal belongs to the triclinic system,space group P1,with a=7.230（3）,b=11.626（5）,c=14.001（6）,α=108.12（0）°,β=95.85（0）°,V=1095.33（157）3,C20H20CoN2O12,Mr=539.31,Z= 2,Dc=1.635 g/cm3,μ=0.855 mm-1,F（000）=554,R=0.0427 and wR=0.1042 for 3883 observed reflections （I 〉 2σ（I））.The title compound features a discrete molecular structure,which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network.Additionally,two different patterns of π-π stacking interactions further consolidate the framework.

两性离子超分子水凝胶的制备及对废水中阴/阳离子染料的吸附去除

以三聚氯氰和5-氨基间苯二甲酸为原料,通过亲核取代制备了一种新型耐盐两性离子超分子水凝胶(ZSH)2,4,6-三(3,5-二羧基苯基氨基)-1,3,5-三嗪。运用FTIR、NMR、MS和SEM技术对ZSH进行了表征,并将其用于对阴离子染料活性艳红(K-2BP)和阳离子红(X-GTL)的吸附去除。基于ZSH的pH响应性和耐盐性,在高盐染料废水中利用ZSH的原位溶胶-凝胶转变,可在其与阴/阳离子染料接触的瞬间完成吸附。当吸附pH为0.86、ZSH与K-2BP的质量比为5∶2时,K-2BP的去除率可达89.6%,饱和吸附量为459.2 mg/g;当吸附pH为1.00、ZSH与X-GTL的质量比为2∶1时,X-GTL的去除率可达91.8%,饱和吸附量为427.6 mg/g。ZSH吸附K-2BP和X-GTL的过程更符合Freundlich等温吸附模型。

超分子化合物[M(4,4'-bipy)_2(H_2O)_4]·(4,4'-bipy)_2·(3,5-diaba)_2·8H_2O](M=Co,Ni,Cd)的合成及晶体结构

合成了3个超分子化合物[M(4,4'-bipy)2(H2O)4]·(4,4'-bipy)2·(3,5-diaba)2·8H2O(M=Co(1),Ni(2),Cd(3);4,4'-bipy=4,4'-联吡啶;3,5-diaba=3,5-二氨基苯甲酸阴离子),用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系,空间群为P2/c。晶体学参数:化合物1:a=0.9389(2)nm,b=0.7751(1)nm,c=3.9284(6)nm,β=90.14(2)°,V=2.85880(69)nm3,Z=4,Dc=1.397g·cm-3,F(000)=1266,μ=0.380mm-1,R1=0.0349,wR2=0.0829;化合物2:a=0.9383(2)nm,b=0.7753(1)nm,c=3.9218(6)nm,β=90.09(1)°,V=2.85280(68)nm3,Z=2,Dc=1.399g·cm-3,F(000)=1268,μ=0.420mm-1,R1=0.0366,wR2=0.0805;化合物3:a=0.94091(13)nm,b=0.77885(11)nm,c=3.9712(5)nm,β=90.10°,V=2.9102(7)nm3,Z=2,Dc=1.433g·cm-3,F(000)=1308,μ=0.454mm-1,R1=0.0468,wR2=0.0964。3,5-diaba未参与配位,在配位阳离子[M(4,4'-bipy)2(H2O)4]2+中,金属离子M髤与来自2个4,4'-bipy的2个氮原子和4个水分子的氧原子配位,呈八面体的几何构型。分子中还存在未配位的4,4'-bipy。通过配位阳离子、游离4,4'-bipy及未配位的3,5-diaba间的丰富氢键,构建成具有三维结构的超分子化合物。

配合物形成的三维超分子体系—[Ni(C_6H_4O_2N)_2(H_2O)_4]的水热法合成、晶体结构及热分析

采用水热法用Ni(NO3)26H2O和异烟酸制备出了一种新的由配合物形成的三维超分子体系—[Ni(C6H4O2N)2(H2O)4],并通过X射线衍射对其晶体结构进行了测定。 该晶体属三斜晶系,空间群为Pī, 所得晶胞参数为: a = 6.9228(4), b = 9.6664(19),c = 6.322(1) , a = 96.86(3), b = 113.33(3), g = 110.35(3)°, V = 347.6(1) 3, Z = 1, Mr = 374.98, Dc = 1.791 g/cm3, F(000) = 194, m = 1.443 mm-1。用1362个可观察的 (I > 2s(I))衍射点,修正123个结构参数, 最终偏离因子R = 0.0444,wR = 0.1271。在组成该化合物的基本结构单元[Ni(C6H4O2N)2(H2O)4]中,Ni处于1个稍微拉长的八面体的中心; 各个结构单元之间通过氢键O H…O相互连接,形成了无限伸展的具有层状结构的三维超分子体系。 另外,从差热及热重曲线可以看出,该化合物加热到154 ℃时开始分解, 首先失去4个H2O,再失去2个异烟酸根,最后残余物为NiO。

超分子化合物{[Mn_2(pda)(phen)_4(H_2O)_2]·2H_2O·2ClO_4^-}的构筑及表征

利用间苯二乙酸、1,10-邻菲啰啉和高氯酸锰在水热条件下反应制备了一种新型超分子配合物{[Mn2(pda)(phen)4(H2O)2]·2H2O.2ClO4-}(H2pda=间苯二乙酸,phen=1,10-邻菲啰啉).通过X单晶衍射测定了晶体结构,并用元素分析、红外光谱等技术对其进行了表征.配合物属3斜晶系,空间群为P-1,a=1.129 0(2)nm,b=1.705 0(2)nm,c=1.734 5(1)nm;α=110.559(1)°,β=107.588(9)°,γ=93.102(12)°;Z=1,R1=0.071 0,wR2=0.202 9.晶体结构分析表明2个锰在1个间苯二己酸的连接下形成了一个双核结构,再在船型六元环氢键和π…π堆积共同作用下,双核结构单元被连成2维网络结构.毗邻的2维结构之间又通过氢键的支撑,拓展为3维网状超分子体系.

1-苯基-3-甲基-4-(6-氢-4-氨基-5-硫杂-2,3-吡嗪)吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过 1 苯基 3 甲基 4 氯乙酰基 吡唑啉酮 5 (PMCP)和氨基硫脲 (TSC)缩合 ,形成了一种含NNS六元杂环的光致变色化合物 (PMCP TSC) .利用元素分析 ,MS ,1HNMR ,IR和UV光谱进行了表征 .通过紫外可见光谱对它的光致变色性质进行了研究 ,测出了光致变色反应的动力学常数 .并用X射线单晶衍射仪测定了PMCP TSC变色后的晶体结构 ,该晶体属单斜晶系 ,具有P2 1/c空间群 ,a =0 .10 5 10 (2 )nm ,b =0 .15 0 6 1(3)nm ,c =0 .99370 (10 )nm ,β =10 7.890 (10 )° ,V =1.496 9(4 )nm3 ,Z =4,Dc=1.417Mg/m3 ,μ =0 .2 32mm-1,F(0 0 0 ) =6 72 ,R =0 .0 334 ,wR =0 .0 896 .结构分析表明 :其光致变色现象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化 .同时该化合物经分子间氢键形成二聚体 ,又通过甲醇与本体分子之间的氢键使化合物形成具有三维网络结构的超分子化合物 .

新型TCAS吸附树脂对水中Cu^(2+)的吸附去除研究

通过静态吸附试验,研究一种由超分子受体化合物磺化硫杂杯芳烃(TCAS)与树脂结合的产物-新型TCAS吸附树脂对重金属Cu2+的吸附去除性能,并初步探讨了吸附机理。试验研究结果表明:当温度为20℃,0.5gTCAS吸附树脂对10 mL浓度为5.0 mg.L-1的Cu2+溶液吸附120 min时,Cu2+的去除率可达到99%以上,pH值对TCAS吸附树脂吸附重金属的影响不大,吸附在TCAS吸附树脂上的Cu2+可洗脱回收,TCAS吸附树脂也可再生利用。

4,4′-联吡啶多钼酸盐的合成、结构与变色性质

通过水热合成法,合成了4,4′-联吡啶多钼酸盐((4,4′-bipyridine)Mo7O22·H2O)单晶超分子化合物.通过元素分析、热重-差热分析(TG-DTA)、粉末X射线衍射(XRD)、单晶X射线衍射、傅里叶变换红外(FTIR)光谱、紫外-可见漫反射光谱(UV-VisDRS)和电子自旋共振(ESR)技术对其组成、热稳定性、结构、光谱和电子特性进行了表征.实验结果表明:该超分子化合物的分子式为C10H12Mo7N2O23,在空气中320℃以下不分解.属于单斜晶系(空间群为P2/n),晶胞参数为a=1.22561(19)nm,b=0.55222(9)nm,c=1.8385(3)nm,β=103.221(2)°,V=1.2113(3)nm3,Z=2和Dc=3.289g·cm-3.基于F2的最终统计:GOF=0.982,R1=0.0228和wR2=0.0557(I>2σ(I)).该单晶超分子化合物由质子化的4,4′-联吡啶阳离子和多金属钼酸盐阴离子[Mo7O22]2-及结晶水组成.它们通过氢键、静电引力和分子间作用力结合在一起的,并构成二维网络结构.样品在光照或加热条件下具有光致变色和热致变色性质.XRD和FTIR证明,变色前后,样品的结构除轻微的畸变外几乎没有变化;而ESR结果表明,光致变色与热致变色的机理可能存在差别.该光致和热致变色的超分子化合物能够为变色机理研究提供参考模型,并在传感器和光敏材料等领域具有潜在应用.