离子对化合物[(IBz)_2Im](TCNQ)的合成与结构表征(英文)

A novel compound [(IBz)2Im](TCNQ) [(IBz)2Im=1,3-bis(4-iodobenzyl) imidazole cation, TCNQ-=7,7,8,8-tetracyanoquinodimethanide anion] was synthesized by the reaction of [(IBz)2Im]Br and LiTCNQ in CH3OH and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a=1.147 35(18) nm, b=2.028 1(3) nm, c=1.264 1(2) nm, β=104.73(0)°, V=2.666(65) nm3, Z=4, C29H19I2N6, Mr= 705.30, Dc=1.757 g·cm-3, R1=0.053 2 and wR2=0.111 2. The structure analysis shows that the anions are stacked into column with isolated π-dimers, and there is one type of TCNQ entries (TCNQ-), in agreement with the IR spectra analysis of the compound. The most prominent structural features are the completely segregated stacking columns of the TCNQ-anions and [(IBz)2Im]+ cations. CCDC: 759523.     

Synthesis and Crystal Structure of a Novel Ion-pair Compound Consisting of 1,3-Bis（4-cynobenzyl） Imidazole Cation and 7,7,8,8-Tetracyanoquinodimethanide Anion

A novel compound [(CNBz)2Im]2(TCNQ)3(CH3CN)((CNBz)2Im = 1,3-bis(4-cyano-benzyl) imidazole cation,TCNQ-1 = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [(CNBz)2Im]Br and LiTCNQ in water and its structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/c with a = 10.1823(17),b = 20.292(3),c = 16.952(3) ,β = 104.73(0)°,V = 3387.6(10)3,Z = 4,C39H24N11,Mr = 646.69,Dc = 1.268 g/cm3,μ = 0.080 mm-1 and F(000) = 1340.The structure was solved by direct methods and refined to R = 0.0596 and wR = 0.0911 for 2690 observed reflections(Ⅰ 2σ(Ⅰ)).The most prominent structural feature is that there are two types of TCNQ entries(TCNQ-1 and TCNQ0) in agreement with the IR spectra analysis of the compound.     

Synthesis and Crystal Structure of a Novel Ion-pair Compound Consisting of 1-（4-Bromobenzyl）pyridinium Cation and 7,7,8,8-Tetracyanoquinodimethanide Anion

The title compound [BrBzPy][TCNQ] （BrBzPy^＋=1-（4-bromobenzyl）pyridinium cation, TCNQ = 7,7,8,8-tetracyanoquinodimethanide anion） was synthesized by the reaction of [BrBzPy]Br and LiTCNQ in ethanol solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.067（3）, b = 7.3089（14）, c = 23.796（4）A, β = 122.011（9）°, V= 2074.6（7）A^3, Z = 4, C24H15BrN5, Mr = 453.32, Dc = 1.451 g/cm^3,μ = 2.002 mm^-1, S = 1.047, F（000） = 916, R = 0.0398 and wR = 0.0921. The most prominent structural features are the completely segregated stacking columns of the TCNQ- anions and [BrBzPy]^＋ cations. In a TCNQ column, the centroid-to-centroid distances of the neighboring anions of TCNQ are 3.2693 and 4.9464 A, respectively.     

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.     

Synthesis and Crystal Structure of a New Complex [Cd（C20H14N4）2Cl2]

The title compound [Cd(C20H14N4)2Cl2] 1 was synthesized via the hydrothermal reaction of CdCl2·7H2O and NaOH with 1,3-bis(benzimidazol-2-yl)benzene (BMB), and characterized by elemental analysis and infrared spectra. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 21.021(6), b = 9.489(3), c = 18.302(6), β = 108.686(6)o, V = 3458.2(19)3, Z = 4, C40H28CdN8Cl2, Mr = 804.01, Dc = 1.544 g/cm3, F(000) = 1624 and μ(MoKα) = 0.829 mm-1. The final R = 0.0306 and wR = 0.0779 for 3334 observed reflections with I > 2σ(I) and R = 0.0796 and wR = 0.0360 for all data. The cadmium atom is four-coordinated by the BMB ligands and Cl atom with a tetrahedral geometry. The extensive N-H···N hydrogen bonding interactions are observed in the structure, which further extend the [Cd(C20H14N4)2Cl2] units into a 1D structure. The thermogravimetric analysis measurement showed that compound 1 has thermal stability as no strictly clean weight loss step occurred below 425 ℃.     

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 ·[SbCl5]2-}2,was synthesized by the hydrothermal reaction of o-diaminobenzene,2-pyridinecarboxylic acid and SbCl3 in 1:1 HCl solution,and characterized by chemical analysis,elemental analysis,IR spectra,thermogravimetric 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 P21/c,with a=16.0397(13),b=14.3189(12),c=15.6370(13),β=105.8980(10)°,V=3454.0(5)3,Z=4,C24H22Cl10N6Sb2,Mr=992.48,Dc=1.909 g/cm3,μ=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.     

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-（2-Pyridyl）benzimidazoleH2]2＋ ·[SbCls]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, Crystal Structure and Luminescent Properties of TbCu（TeO3）2Cl

TbCu(TeO3)2Cl was obtained in high yield from high temperature solid-state reac-ion of Tb4O7,CuO,CuCl2 and TeO2 in a 1:2:2:8 molar ratio at 710 ℃ in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. The title compound crystal-lizes in monoclinic,space group P21/c,with a=5.409(2),b=14.994(6),c=9.183(4),β= 98.884(5)°,V=735.8(5) ?3 and Z=4. TbCu(TeO3)2Cl is isostructural with LnCu(TeO3)2X (Ln= Dy,X= Cl; Ln=Er,X=Cl,Br). Its structure features a three-dimensional (3D) network built from Tb(Ⅲ) and Cu(II) ions interconnected by tellurite and chloride anions; the chloride anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels in the network. Solid-state luminescent spectrum of TbCu(TeO3)2Cl shows a strong emission band at 545 nm with a luminescent life time of 291 μs.     

Synthesis, Crystal Structure and Properties of a Dinuclear Cobalt（II） Complex [Co2（a-furacrylato）4（Phen）2（H2O）]·C2H5OH

A dinuclear cobalt(Ⅱ) complex [Co2(α-furacrylato)4(Phen)2(H2O)]·C2H5OH has been synthesized with α-furacrylic acid and 1,10-phenanthroline as the ligands, and its crystal structure was determined. The crystal is of monoclinic system, space group C2/c with a=1.07388(8), b=2.4300(2), c=1.86708(14)nm, β=104.3830(10)o, V=4.719.4(7) nm3 , Dc=1.503 g/cm3 , Z=2, F(000)=2196, GOOF=1.053, the final R=0.0343 and wR=0.0883. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked by the bridging coordination of two α-furacrylic acid anions and one water molecule, and their end positions are respectively coordinated with two 1,10-phenanthroline molecules and two α-furacrylic acid anions, forming a dinuclear structure. Both cobalt(Ⅱ) ions adopt hexa-coordinated distorted octahedral geometry. The electrochemical and fluorescence properties of the title complex are also discussed.     

Hydrothermal Synthesis, Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH2]2+·[SbCl5]2-}2

A new supramolecular compound, {[2-(2-pyridyl)benzimidazoleH2]2 ·[SbCl5]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylic acid and SbCl3 in 1:1 HCl solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetric 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 P21/c, with a = 16.0397(13), b = 14.3189(12), c = 15.6370(13) (A), β = 105.8980(10)°, V = 3454.0(5) (A)3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3, μ = 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…C1.Moreover,the compund adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-(2-pyridy1)benzimidazole divalent cations.The title compound also shows godd fluorescent behaviors.     

基于7,7,8,8-四氰基对醌二甲烷-氯化锰反应的二价锰配合物的合成,晶体结构和磁性(英文)

以氯化锰、双二苯基膦酸甲烷(dppm)及7,7,8,8-四氰基对醌二甲烷(TCNQ)为原料,合成了标题化合物[Mn(dppmdo)_3][(TCNQ)(DCBE)]1;利用X射线衍射、红外光谱、紫外-可见-近红外光谱和循环伏安等技术对合成产物进行了表征.结果表明,化合物1在近红外区发生配体TCNQ之间的电子转移(TCNQ/TCNQ~-).化合物1中的TCNQ比游离态的TCNQ分子更容易被还原.室温下,化合物1的有效磁矩(12.7μB)远高于预期的由一个高自旋Mn~(2+)离子(S=5/2)、一个TCNQ(S=1/2)阴离子及一个DCBE(S=1/2)阴离子组成基团的有效磁矩(4.58μB),表明它们之间存在着很强的磁相互作用.     

(TCNQ)22-基氢键分子磁体表现出非常强的反铁磁偶合作用

合成并表征了一种新的离子对化合物[4-NH2-Py][TCNQ](其中4-NH2-Py+是4-氨基吡啶阳离子,TCNQ-为7,7,8,8-四氰基对苯二醌二甲烷自由基阴离子)。在该离子对化合物晶体中,2个TCNQ-离子形成了面对面堆积的二聚体;阴离子中的氰基分别和阳离子上的氨基、吡啶质子化氮原子之间存在非常强的分子间氢键。通过氢键作用,相邻的TCNQ-二聚体被阳离子连成三维氢键网络。变温磁化率测量表明,在2～400 K温度范围内,该离子对化合物表现为抗磁性。在密度泛函理论框架下,用对称性破损方法计算了化合物晶体中π二聚体内以及通过氢键连接的相邻的TCNQ-离子之间的磁交换常数,发现π二聚体内存在非常强的反铁磁交换作用,与之相比,通过氢键连接的TCNQ-离子之间的磁交换作用可以忽略。π二聚体内强反铁磁交换作用(J/kB≈1805 K)导致了该化合物基本表现为抗磁性。     

The first coordination compound containing three different types of spin carriers: 2p-3d-4f (TCNQ.-, Cu2+ and Gd3+)

A novel heterospin system, [(CuL)2Gd(TCNQ)2].TCNQ-.CH3OH.2CH3CN, is obtained by reacting the mononuclear complex, [CuL], with gadolinium(III) nitrate, followed by the substitution of the nitrato ions with anionic organic radicals.     

Analysis of active chemical species generated by electrolysis using non-aqueous capillary electrophoresis. Detection of the anion radical and the divalent anion of tetracyanoquinodimethane

We have investigated detection of the anion radical and the divalent anion of tetracyanoquinodimethane (TCNQ) by acetonitrile-CE under anaerobic conditions. With electrolysis at a potential of 0.0 V (vs. Ag/AgCl), an acetonitrile solution of TCNQ turned green, characteristic of the TCNQ anion radical (TCNQ-). Only one peak of the anionic compound was observed in CE of the electrolysis solution and it should be that of TCNQ-. Then, the electrolysis potential was shifted to -0.8 V expected to be sufficient potential for the further reduction of TCNQ-, and the solution turned almost colourless. In CE analysis of the latter solution, another anionic component possessing a larger electrophoretic mobility than that of TCNQ- was detected, and it was decomposed immediately under aerobic conditions. This product was strongly suggested to be the divalent anion of TCNQ, and the present method would contribute notably to detection of the unstable species.     

Hexaazamacrocyclic nickel and copper complexes and their reactivity with tetracyanoquinodimethane

The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N6, forms mono- and dinuclear derivatives with copper chloride depending on the reaction stoichiometries and times. The mononuclear derivative, [Cu([18]ane-N6)]Cl2.H2O, presents the macrocycle wrapped around the metal atom in a distorted octahedral coordinative environment, while the dinuclear derivative, [Cu2([18]ane-N6)Cl2]Cl2.4H2O, is formed by a central Cu2Cl2 core surrounded by an almost planar macrocycle. The crystal structure of both derivatives is stabilized by a network of hydrogen bonds involving the amine macrocyclic groups, the chloride anions, and the crystallization water molecules. The copper atoms in the dinuclear derivative show a strong antiferromagnetic coupling, as expected for the crystal structure parameters. A mononuclear nickel derivative has also been obtained from nickel nitrate by following the same synthetic procedure. These compounds react with TCNQ salts with formation of two types of derivatives, [M([18]ane-N6)](TCNQ)2 and [M([18]ane-N6)](TCNQ)4, depending on the use of radical-anionic or mixed-valence TCNQ salts in the reaction. The crystal structures of the nickel derivatives show that the former derivatives are built up by macrocyclic metal cations surrounded by dimeric dianions (TCNQ)22-, either isolated or stacked along the crystal. The derivative with four TCNQ units/formula consists of alternated chains of metallomacrocyclic cations and stacked TCNQ anions. The crystal parameters suggest that every TCNQ holds approximately 0.5 electrons and overlaps with a neighboring unit to form dimeric monoanions, (TCNQ)2-.     

Ruthenium(II) complexes of 2-benzoylpyridine-derived thiosemicarbazones with cytotoxic activity against human tumor cell lines

Reaction of [RuCl(3)(dppb)H(2)O] (dppb=1,4 bis(diphenylphospine)butane) with 2-benzoylpyridine thiosemicarbazone (H2Bz4DH) and its N(4)-methyl (H2Bz4M) and N(4)-phehyl (H2Bz4Ph) derivatives gave [RuCl(dppb)(H2Bz4DH)]Cl (1), [RuCl(dppb)(H2Bz4M)]Cl (2) and [RuCl(dppb)(H2Bz4Ph)]Cl (3). The cytotoxic activity of the studied compounds was tested against the MCF-7, TK-10 and UACC-62 human tumor cell lines. The precursor [RuCl(3)(dppb)H(2)O] exhibits cytocidal activity against the tree cell lines. H2BzDH, H2Bz4M, and [RuCl(dppb)(H2Bz4M)]Cl (2) show a selective cytocidal effect against the UACC-62 cell line which makes them the most promising compounds.     

N(4)-tolyl-2-benzoylpyridine-derived thiosemicarbazones and their palladium(II) and platinum(II) complexes: Cytotoxicity against human solid tumor cells

Complexes [Pt(2Bz4oT)Cl], [Pt(2Bz4mT)Cl], and [Pt(2Bz4pT)Cl] were prepared with N(4)-ortho-(H2Bz4oT), N(4)-meta-(H2Bz4mT), and N(4)-para-(H2Bz4pT) tolyl-2-benzoylpyridine-derived thiosemicarbazones. The thiosemicarbazones exhibited moderate anti-proliferative activity against HepG2 (hepatoma) and UACC-62 (melanoma) cancer cell lines, but showed high anti-proliferative effect against A431 (epithelial carcinoma) cancer cell lines. Upon coordination to platinum(II) the anti-proliferative activity decreases in all cases. The cytotoxicity of the previously prepared palladium(II) analogues [Pd(2Bz4oT)Cl], [Pd(2Bz4mT)Cl], and [Pd(2Bz4pT)Cl] was also investigated. As in the case of the platinum(II) complexes, coordination to palladium(II) did not lead to activity improvement. Investigations on the mechanism of cytotoxic action against A431 cells revealed that [Pd(2Bz4oT)Cl] induced DNA fragmentation and apoptosis while H2Bz4oT did not present this effect. The high anti-proliferative effect of the thiosemicarbazones and [Pd(2Bz4oT)Cl] against A431 cells, together with the pro-apoptotic effect of [Pd(2Bz4oT)Cl] suggests that these compounds have potential as chemotherapeutic drug candidates.