两个喹啉酰腙镉配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了配合物[Cd(L)(H₂O)(NO₃)₂] (1)和[Cd(L)I₂]·CH₃OH (2)(L=喹啉-8-甲醛对羟基苯甲酰腙)。单晶衍射结果表明,在配合物1中,Cd(Ⅱ)分别与1个三齿配位的酰腙配体,1个水分子,1个单齿配位和1个双齿配位的硝酸根配位,从而拥有单帽三棱柱配位构型。然而,配合物2中,Cd(Ⅱ)离子采取扭曲的四方锥配位构型,与来自配体L的N₂O电子供体以及2个碘离子配位。此外还详细研究了配合物1和2的热稳定性及荧光性质。     

两个喹啉酰腙镉配合物的合成、结构及荧光性质

合成并通过单晶衍射表征了配合物[Cd(L)(H₂O)(NO₃)₂](1)和[Cd(L)I₂]·CH₃OH(2)(L=喹啉-8-甲醛对羟基苯甲酰腙)。单晶衍射结果表明,在配合物1中,Cd(Ⅱ)分别与1个三齿配位的酰腙配体,1个水分子,1个单齿配位和1个双齿配位的硝酸根配位,从而拥有单帽三棱柱配位构型。然而,配合物2中,Cd(Ⅱ)离子采取扭曲的四方锥配位构型,与来自配体L的N₂O电子供体以及2个碘离子配位。此外还详细研究了配合物1和2的热稳定性及荧光性质。     

两个吡咯酰腙铜配合物的制备、结构及抗肿瘤活性

合成并通过X-射线单晶衍射表征了2个铜配合物[Cu(H₂L)₂(THF)] (1)和[Cu₂(L)Cl(CH₃OH)]·H₂O (2) (H₃L=3,4-二甲基吡咯-5-甲酰基-2-甲酸乙酯-2-羟基-4-甲基苯甲酰腙)。结果表明在配合物1中, 中心金属离子与周围2个提供N₂O配位原子的酰腙阴离子和1个四氢呋喃分子配位, 具有扭曲的四方锥配位构型。然而, 在双核配合物2中, 酰腙配体脱去3个质子, 通过NO和N₂O₂配位原子分别桥联2个具有平面正方形配位构型的铜中心。2个配合物对人肺癌细胞A549, 人食管癌细胞ECA109和人胃癌细胞SGC7901展现出显著的抗肿瘤活性。     

N'-(2-羟基-5-甲氧基苯甲基)-4-二甲氨基苯甲酰肼及其氧钒(V)配合物:合成、晶体结构和脲酶抑制活性

制备了一个苯甲酰腙化合物N'-(2-羟基-5-甲氧基苯甲基)-4-二甲氨基苯甲酰肼(H₂L).利用H₂L、乙酰氧肟酸(HAHA)和VO(acac)₂在甲醇中反应得到了配合物[VOL(AHA)].通过元素分析、红外和紫外光谱,以及单晶X-射线衍射对H₂L和其配合物进行了表征。苯甲酰腙配体作为二价阴离子,利用其酚羟基氧原子、亚胺基氮原子、以及烯醇氧原子与V原子进行配位.乙酰氧肟酸配体利用其羰基氧原子和去质子化的羟基氧原子进行配位.配合物中的V原子为八面体配位构型。测试了H₂L、HAHA和钒配合物的脲酶抑制活性.在浓度为100 μmol·L^-1时,钒配合物对幽门螺旋杆菌脲酶的抑制率为63%,其IC₅₀值为45μmol·L^-1.还利用分子对接技术研究了配合物分子与脲酶的作用方式.     

N'-(2-羟基-5-甲氧基苯甲基)-4-二甲氨基苯甲酰肼及其氧钒(Ⅴ)配合物:合成、晶体结构和脲酶抑制活性

制备了一个苯甲酰腙化合物N'-(2-羟基-5-甲氧基苯甲基)-4-二甲氨基苯甲酰肼(H₂L)。利用H₂L、乙酰氧肟酸(HAHA)和VO(acac)₂在甲醇中反应得到了配合物[VOL(AHA)]。通过元素分析、红外和紫外光谱,以及单晶X-射线衍射对H₂L和其配合物进行了表征。苯甲酰腙配体作为二价阴离子,利用其酚羟基氧原子、亚胺基氮原子、以及烯醇氧原子与V原子进行配位。乙酰氧肟酸配体利用其羰基氧原子和去质子化的羟基氧原子进行配位。配合物中的V原子为八面体配位构型。测试了H₂L、HAHA和钒配合物的脲酶抑制活性。在浓度为100μmol·L^-1时,钒配合物对幽门螺旋杆菌脲酶的抑制率为63%,其IC₅₀值为45μmol·L^-1。还利用分子对接技术研究了配合物分子与脲酶的作用方式。     

萘啶酮的单核和双核银配合物的合成与晶体结构

合成了萘啶酮的单核和双核银配合物Ag₂(L₁)₂(HL₁=5，7-二甲基-1，8-萘啶-2-酮) (1)和[Ag(HL₂)(PPh₃)₂]·2H₂O(H₂L₂=1，8-萘啶-2,7-二酮) (2)。并通过元素分析，红外光谱及X-射线单晶衍射对其进行了结构表征。配合物1的晶体属单斜晶系，P1空间群。中心金属银为三配位T型几何构型，Ag-Ag间距离为0.274 8(2) nm，具有强的Ag…Ag作用。配合物2的晶体属三斜晶系，P2₁/n空间群。银与1个氮原子及2个磷原子形成三配位结构。     

丙二酰二腙衍生的二氧化二钼(Ⅵ)配合物的合成、表征和晶体结构

本文报道了二氧杂钼(Ⅵ)配合物[MoO₂(H₂L)(H₂O)]的合成、表征和分子结构。该配合物是由马来酰二腙配体双(2-羟基-1-萘醛)丙二酰二腙(H₄L)与双(乙酰丙酮)二氧钼(Ⅵ)在甲醇中以1∶1的物质的量之比反应得到的。通过各种光谱(如IR、MS和NMR)对该配合物进行了表征。通过单晶X射线晶体学确定了配合物的结构。该配合物属于单斜晶系P2₁/c空间群。金属中心具有扭曲的八面体配位环境,与H₂L^2-的1个甲亚胺氮原子、2个末端氧基团、H₂L^2-的2个氧原子和配位水分子的1个氧原子相连。     

丙二酰二腙衍生的二氧化二钼(Ⅵ)配合物的合成、表征和晶体结构

本文报道了二氧杂钼(Ⅵ)配合物[MoO₂(H₂L)(H₂O)]的合成、表征和分子结构。该配合物是由马来酰二腙配体双(2-羟基-1-萘醛)丙二酰二腙(H₄L)与双(乙酰丙酮)二氧钼(Ⅵ)在甲醇中以1∶1的物质的量之比反应得到的。通过各种光谱(如IR、MS和NMR)对该配合物进行了表征。通过单晶X射线晶体学确定了配合物的结构。该配合物属于单斜晶系P2₁/c空间群。金属中心具有扭曲的八面体配位环境,与H₂L^2-的1个甲亚胺氮原子、2个末端氧基团、H₂L^2-的2个氧原子和配位水分子的1个氧原子相连。     

基于4-氟-N'-（3-乙氧基-2-羟基苯亚甲基）苯甲酰肼的甲基麦芽酚和乙基麦芽酚配位的氧钒（Ⅴ）配合物的合成、晶体结构及其类胰岛素活性

制备了一个芳酰腙化合物4-氟-N''-（3-乙氧基-2-羟基苯亚甲基）苯甲酰肼（H₂L）。利用H₂L和VO（acac）₂分别与甲基麦芽酚（mat）和乙基麦芽酚（Emat）在甲醇中反应,得到了2个配合物[VO（L）（mat）]（1）和[VO（L）（Emat）]（2）。通过元素分析、红外光谱、紫外可见光谱和核磁共振氢谱表征了这些化合物的结构。通过单晶X射线衍射进一步确定了化合物的结构。芳酰腙配体以二价阴离子的方式通过酚羟基氧、亚胺基氮和烯醇氧原子与钒原子进行配位。在每个配合物中,钒都采取八面体配位构型。将配合物通过灌胃对正常的大鼠和四氧嘧啶糖尿病大鼠给药2周时间,结果表明这两个配合物在剂量为10.0和20.0 mgV·kg^-1时可以显著降低四氧嘧啶糖尿病大鼠的血糖值,而对于正常大鼠的血糖值却没有改变。     

基于4-氟-N'-(3-乙氧基-2-羟基苯亚甲基)苯甲酰肼的甲基麦芽酚和乙基麦芽酚配位的氧钒(Ⅴ)配合物的合成、晶体结构及其类胰岛素活性

制备了一个芳酰腙化合物4-氟-N''-（3-乙氧基-2-羟基苯亚甲基）苯甲酰肼（H₂L）。利用H₂L和VO（acac）₂分别与甲基麦芽酚（mat）和乙基麦芽酚（Emat）在甲醇中反应,得到了2个配合物[VO（L）（mat）]（1）和[VO（L）（Emat）]（2）。通过元素分析、红外光谱、紫外可见光谱和核磁共振氢谱表征了这些化合物的结构。通过单晶X射线衍射进一步确定了化合物的结构。芳酰腙配体以二价阴离子的方式通过酚羟基氧、亚胺基氮和烯醇氧原子与钒原子进行配位。在每个配合物中,钒都采取八面体配位构型。将配合物通过灌胃对正常的大鼠和四氧嘧啶糖尿病大鼠给药2周时间,结果表明这两个配合物在剂量为10.0和20.0 mgV·kg^-1时可以显著降低四氧嘧啶糖尿病大鼠的血糖值,而对于正常大鼠的血糖值却没有改变。     

Synthesis, structures and luminescent properties of Co(II) and Ni(II) metal-organic frameworks with semirigid diphthalic ligands

A series of transition metal coordination polymers [Co(H₃L)₂(4,4′- bpy)(H₂O)₂]_n?n(4,4′-bpy) (1), [Ni(H₂L)(4,4′-bpy)(H₂O)₂]_n (2), [Co₂(L)(phen)₂(H₂O)₄]_n?(H₂O)_2n (3), and [Ni₂(L)(phen)₂(H₂O)₄]_n?(H₂O)_2n (4) have been assembled from a semirigid multicarboxylate ligand 3,3′-(1,4-phenylenebis(oxy))diphthalic acid (H₄L) with the help of 4,4′-bipyridine (4,4′-bpy) ligand or 1,10-phenanthroline (phen) ligand. X-ray single crystal diffraction analysis reveals that complex 1 crystallizes in the space group of P − 1 and displays a one-dimensional (1D) chain structure constructed from 4,4′-bpy ligand and H₃L ligand, which was further interlinked to form a three-dimensional network via hydrogen bonds. In complex 2, Ni(II) atoms are coordinated by L ligand in monodentate fashion to form alternate left- and right-helices, which are further bridged together by the coordination interactions between Ni(II) atoms and 4,4′-bpy, leading to a 2-fold (4, 4)-connected interpenetrating network. Isostructural complexes 3 and 4 belong to the space group P − 1 and display a 1D chain structure constructed from phen and L ligands, which was further interlinked to form a 2D plane via π–π interactions. In addition, their thermal and luminescent properties were also investigated.     

pH-dependent Co(II) assemblies from achiral 2-benzothiazolylthioacetic acid: crystal structures,symmetry breaking,and magnetic properties

Based on an achiral 2-benzothiazolylthioacetic acid (HL) ligand, three Co(II) coordination compounds, {[Co(L)₂(H₂O)₃]·H₂O}_n (1), [Co(L)₂(H₂O)₂]_n (2), and [Co(L)₂(H₂O)₄]·2H₂O (3), were obtained under different pH environments. Compound 1 possessing an interesting chiral 1-D helical double chain was synthesized with pH of 5.0~6.5, and the chiral symmetry breaking has been probed by single-crystal X-ray diffraction and circular dichroism spectroscopy. Switching pH to 4.0~5.0 and 3.0~4.0 resulted in achiral 2 and 3, respectively. Compound 2 has a 1-D chain structure and 3 is mononuclear.     

Synthesis,Structure, and Properties of Nickel(II) and Cobalt(II) Coordination Compounds with Optically Active Diaminodioxime (H2L) Derived from 3-Carene. Molecular and Crystal Structures of the [Ni(H2L)(NO3)]NO3 and [Ni(HL)]ClO4 · H2O Complexes

Nickel(II) and cobalt(II) complexes with optically active diaminodioxime (H₂L, the derivative of 3-carene) of the compositions [Ni(H₂L)NO₃]NO₃ (I), Ni(H₂L)Cl₂ (II), [Ni(HL)]ClO₄ · H₂O (III), and Co(H₂L)Cl₂ (IV), were synthesized. According to X-ray diffraction data, the structures of the paramagnetic compound I and diamagnetic complex III are ionic. In the cation of I, the distorted NiN₄O₂ octahedron is formed by the N atoms of the tetradentate cyclic ligand (H₂L molecule) and by the O atoms of NO₃ ^–; anion functioning as bidentate cyclic ligands. In the cation of III, the NiN₄ coordination unit is a distorted square formed upon coordination of the tetradentate cyclic ligand, HL^–; anion. The data of magnetochemistry and UV-Vis, IR, and Raman spectroscopy suggest that paramagnetic complexes II and IV contain a distorted octahedral polyhedron MCl₂N₄ (M = Ni, Co).     

Self-assembly of three Cd(II) complexes: 0-D, 1-D,and 3-D structures based on 2-(1H-imidazol-1-methyl)-1 H-benzimidazole

Three new complexes, [Cd(L)I₂]₂ (1), {[Cd(L)I₂]?·?DMF} _n (2), and [Cd₂(L)₄(μ ₂-I)I(H₂O)] _n (3), have been obtained through self-assembly of an unsymmetrical ligand 2-(1H-imidazol-1-methyl)-1H-benzimidazole (L) with Cd(II) salts. Single-crystal X-ray diffraction shows that 1 displays a dimeric structure in which two Cd(II) ions are bridged by two bidentate bridging L. Complex 2 exhibits a 1-D chain structure (···Cd–L–Cd–L···) constructed by L bridging Cd(II) ions. In 3, the Cd(II) ions are five-connected nodes and linked by L and iodide leading to the 3-D network. Complexes 2 and 3 are synthesized maintaining the same solvents and stoichiometric ratio of metal and ligand at different reaction temperature. The different structures of the complexes indicate that the temperature plays a significant role in construction of the complexes. Luminescent properties of 1–3 have been investigated in the solid state at room temperature.     

由2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的过渡金属配位聚合物的合成、结构及性质

在溶剂热条件下,由2-(4′-羧基苯基)咪唑-4,5-二羧酸(H_4L,C_(12)H_8N_2O_6),合成了4个配位聚合物{[M(H_3L)_2]·2H_2O}_n(M=Zn(1),Cd(2),Co(3)),[Cd(H_2L)(H_2O)]_n(4)。用元素分析、红外光谱、热重分析和单晶X射线衍射对配合物进行了表征和结构分析。结构分析结果表明:1～3是异质同晶。配体失去1个质子以H_3L~-的形式通过单齿和N,O-双齿螯合的配位模式与中心金属离子配位,构成一个略有变形的八面体结构。对于配合物4来说,配体失去2个质子以H_2L~(2-)的形式分别通过单齿和N,O-双齿螯合的配位方式与Cd~(2+)配位,中心离子采取扭曲的七配位五角双锥配位模式,并且通过配体苯环上羧基氧原子的双齿桥联作用连接2个中心离子,形成四元环的双核结构;同时呈现双节点(3,6)-连接的二维拓扑网络(4.4.4)(4.4.4.4.4.4.5.6.6.6.6.6)。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

Heterobinuclear and Heterotrinuclear complexes of Oxorhenium(V) with Cu(II), Ni(II), Fe(III), UO2(VI) and Th(IV) in the solid state

New heteronuclear complexes containing oxorhenium(V), Cu(II), Ni(II), Fe(III), UO₂(VI) and Th(IV) ions were prepared by the reaction of the complex ligand, [ReO(H₄L)Cl]Cl₂, where H₄L = 8,17-dimethyl-6,15-dioxo-5,7,14,16-tetrahydrodibenzo[a,h][14]annulene-2,11-dicarboxylic acid, with the previous transition and actinide salts. Three heteronuclear Cu(II) complexes were isolated depending on the ratio of [ReO(H₄L)Cl]Cl₂?:?Cu(II) ion. When the ratios were 1?:?0.5, 1?:?1 and 1?:?2, the heteronuclear complexes {[ReO(H₃L)Cl]₂CuCl₂(OH₂)₂}SO₄ · H₂O (I), [ReO(H₃L)Cl₂Cu(OH₂)₂(SO₄)] (II) and {ReO(H₂L)Cl[Cu(OH₂)₃ SO₄]₂} (III) were obtained, respectively. Heteronuclear complexes of the other metal cations were obtained by mixing [ReO(H₄L)Cl]Cl₂ with the metal salt in the ratio 1?:?1 to obtain the heteronuclear complexes [ReO(H₃L)Cl₂Ni(OH₂)₂](NO₃)₂ (IV), [ReO(H₃L)Cl₃Fe(OH₂)₃](NO₃)₂ (V), [ReO(H₃L)ClUO₂(NO₃)₂ (OH₂)]Cl (VI) and [ReO(H₃L)Cl₃Th(NO₃)₂(OH₂)]NO₃ · 2H₂O (VII). The complex ligand coordinates with the heterometal ion via the carboxylate group, and the infrared bands ν_as COO and ν_s COO indicate that the carboxylate acts as a unidentate ligand to the heterometal cations. Cu(II) and Fe(III) cations in the heteronuclear complexes have octahedral geometry, while Ni(II) is square planar. Thermal studies explored the possibility of obtaining new heteronuclear complexes pyrolytically in the solid state from the corresponding mother complexes. The structures of the complexes were elucidated by conductance, IR and electronic spectra, magnetic moments, ¹H NMR and TG-DSC measurements as well as by mass spectroscopy.     

Three Cd(II) coordination polymers based on a pyridyldicarboxylate: effect of coordinated water

Abstract

By systematic change of the solvothermal synthesis, three new coordination polymers, [Cd(L)?(H₂O)]?2H₂O (1), [Cd(L)?(H₂O)]?H₂O (2), and [Cd(L)] (3), have been synthesized based on a tritopic ligand 4-(pyridin-3-yl)isophthalic acid (H₂L). Compounds 1 and 2 show very similar two-dimensional (2D) bilayers further linked by interlayer hydrogen bonds into three-dimensional (3D) supramolecular structures, while 3 displays a 3D structure constructed form one-dimensional (1D) Cd-carboxyl chains. Notably, 1 and 2 have a pair of unusual isomers with the opposite orientation of coordinated H₂O on the metal centers, leading to different hydrogen bonding interactions. Thermal stabilities and solid-state photoluminescences for 1–3 were also investigated.     

A series of 1-D, 2-D and 3-D coordination polymers self-assembled from a flexible dicarboxylate and mixed N-donor ligands: syntheses,structural diversity,and luminescent properties

We have synthesized a series of metal–organic coordination frameworks under solvothermal conditions, formulated as [Cu(L)(phen)](1), [Co₂(L)₂(bib)]·CH₃OH(2), [Co(L)(btmb)_0.5](3), [Zn(L)(bib)]·2H₂O(4), [Cu(L)(bib)]·DMF(5), and [Mn₄(L)₄(bimb)(CH₃OH)](6) based on a flexible multicarboxylic bridging ligand 4,4′-methylenebis(oxy)-dibenzoic acid (H₂L) and flexible N-donor ligands 1,4-bis (1H-imidazol-1-yl)-butane (bib), 1,4-bis(1H-1,2,4-triazol- 1-ylmethyl)benzene (btmb), and 1,4-bis(1H-imidazol-1-ylmethyl)benzene (bimb). The structures of the frameworks have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. The crystal structure determinations reveal that 1 has a 1-D Z-shape chain. Compounds 2 and 3 are 2-D twofold parallel interpenetrating 4-connected net with the Schläfli symbol {4⁴·6²}. Compound 4 is a 2-D threefold parallel interpenetrating 4-connected nets with the Schläfli symbol {4⁴·6²}. Compound 5 is 3-D 4-connected net with the Schläfli symbol {6⁵·8}. Compound 6 is characterized by a three-dimensional framework with one-dimensional homogeneous Mn-carboxylate chain. We found that flexible carboxylate ligands have different coordination modes under different synthetic conditions. The flexible skeleton of ligands and the coordination angle between the ligand and the metal ion is described. The luminescence and thermogravimetric properties of these compounds have been investigated.     

基于6-羟基-2-吡啶基膦酸配体的铜配合物的合成、结构及磁性

在水热条件下, 以6-羟基-2-吡啶基膦酸为主配体, 4, 4′-联吡啶(bpy)及1, 2-二(4-吡啶基)乙烯(bpe)为桥联配体, 合成了2个铜膦酸配位聚合物[Cu₃(L)₂(bpy)₂(H₂O)₂]· 2H₂O (1), [Cu₃(L)₂(bpy)₂(H₂O)₃]· 2H₂O (2)。配合物1中, Cu²⁺离子由膦酸配体连接成一条链, 该链由bpy桥联成二维层, 层与层之间通过氢键作用构成三维结构。配合物2与配合物1是同构的, 桥联配体是bpe。磁性研究表明, 配合物1与2中铜离子之间存在反铁磁性耦合。