通过铜(Ⅱ)、铁(Ⅲ)和铁(Ⅱ)与2,2'-联咪唑协同作用构筑的超分子及其结构的研究

在水和乙醇溶剂中,通过Cu(Ⅱ),Fe(Ⅲ)和Fe(Ⅱ)与2,2'-联咪唑协同作用,构筑了四种新的超分子配合物[Cu(H2biim)(gly)(H2O)]Cl·H2O(1),[Cu(H2biim)(C3H2O4)(H2O)]·1.5H2O(2),[Fe2(μ-O)(H2biim)4(H2O)2](NO3)4·C2H5OH(3)和[Fe(H2biim)3]SO4(4)(H2biim=2,2'-联咪唑;gly-=甘氨酸根;C3H2O24-=丙二酸根).并通过元素分析,红外光谱和X射线单晶衍射对其组成、结构和谱学性质进行研究.H2biim配体,丙二酸根和甘氨酸根三种配体都采用了双齿螯合方式与金属离子配位.配合物1～4中,通过H2biim配体的N-H键与阴离子、水分子和溶剂分子形成多种氢键,如R12(7),R22(9)和R12(4)等,以及H2biim配体之间的π-π堆积,阳离子不对称单元构筑了多维结构的超分子配合物.     

基于3，5-二硝基苯甲酸和2，2'-联吡啶的Cu(Ⅱ)、Zn(Ⅱ)配合物的合成及晶体结构

以3,5-二硝基苯甲酸(3,5-Hdnbc)和2,2'-联吡啶(2,2'-bipy)为配体,与Zn²⁺和Cu²⁺反应,得到了4个配合物[Zn(3,5-dnbc)₂(2,2'-bipy)(H₂O)]·(3,5-Hdnbc)(1),[Cu(3,5-dnbc)₂(2,2'-bipy)(H₂O)](2),[Cu(2,2'-bipy)₂(3,5-dnbc)](NO₃)·2(3,5-Hdnbc)(3),和[Cu(2,2'-bipy)₂Cl](3,5-dnbc)·(3,5-Hdnbc)(4)。用元素分析、红外光谱对其进行了表征,并用单晶X-射线衍射测定了配合物的晶体结构;对配合物1和2进行了热重分析。4个配合物均为单核分子。配合物1中,Zn²⁺离子是五配位的三角双锥结构;配合物2中,Cu²⁺离子是五配位的变形四方锥结构;配合物3和4中,Cu²⁺离子均是五配位的三角双锥结构;配合物中存在氢键和π-π堆积等弱的分子间作用力。     

Phen-铜(II)-氨基酸配合物的合成、表征及其SOD活性

合成了3个新的SOD模拟配合物：[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O (1)、[Cu(Phen)(L-Ala)(H₂O)]Cl·4H₂O (2)、[Cu(Phen)(L-Thr)(H₂O)]Cl·2H₂O (3) [Phen(1，10-邻菲咯啉)、L-Gln(谷氨酰胺)、L-Ala(丙氨酸)、L-Thr(苏氨酸)]。用元素分析、摩尔电导、红外光谱、紫外-可见光谱对配合物进行了表征。用X-射线衍射对配合物[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O的晶体结构进行了测定。用氯化硝基四氮唑蓝(NBT)光还原法对这3个配合物催化歧化超氧阴离子自由基(O₂^{- ·})的能力进行了测定。结果表明：这些配合物具有较高的SOD活性， 催化速率常数K_Q分别为1.58 × 10⁷ mol^-1·L·s^-1、5.65 × 10⁷ mol^-1·L·s^-1、0.83 × 10⁷ mol^-1·L·s^-1。     

基于醚氧桥联四羧酸配体构筑的三个钴(Ⅱ)、铜(Ⅱ)和镉(Ⅱ)配位聚合物的合成、结构和在Knoevenagel缩合反应中的催化性质

采用水热方法,选用醚氧桥联四羧酸配体H₄dia与菲咯啉(phen)、2,2''-联吡啶(bipy)或双(4-吡啶基)胺(bpa)分别与CoCl₂·6H₂O、CuCl₂·2H₂O和CdCl₂·4H₂O在160℃下反应,得到了一个一维链结构[Co₂(μ4-dia)(phen)2(H₂O)₂]_n(1)和2个三维网络结构的配位聚合物[Cu₂(μ6-dia)(bipy)₂]_n(2)和{[Cd₂(μ5-dia)(μ-bpa)2(H₂O)]·H₂O}_n(3),并对其结构和催化性质进行了研究。研究表明,在50℃下配合物2在Knoevenagel缩合反应中显示出很好的催化活性。     

1-乙基-6-氟-1，4-二氢-4-氧代-7-(1-哌嗪基)-3-喹啉羧酸-铜(Ⅱ)-多吡啶配合物的合成、表征及与DNA作用

合成了4个新的诺氟沙星(NFA)-铜(Ⅱ)-多吡啶 配合物：[Cu(NFA)(phen)(H₂O)](ClO₄)₂ (1),[Cu(NFA)(tatp)(H₂O)](ClO₄)₂ (2), [Cu(NFA)(dppz)(H₂O)](ClO₄)₂·H₂O (3)和[Cu(NFA)(n-phen)(H₂O)](ClO₄)₂ (4)[NFA=1-乙基-6-氟-1,4-二氢-4-氧代-7-(1-哌嗪基)-3-喹啉羧酸,phen=1,10-邻菲咯啉,tatp=1,4,8,9-四氮三联苯,dppz=二吡啶并[3,2-a;2′,3′-c]吩嗪,n-phen=5-硝基-1,10-邻菲咯啉]。用元素分析、摩尔电导率、红外光谱及紫外可见光谱对配合物进行了表征,推测了配合物的可能结构。应用紫外光谱、荧光光谱及粘度测定方法研究了配合物与CT-DNA的作用,发现这些配合物均以插入方式与CT-DNA作用。采用打孔法研究了配合物的抗菌活性,结果表明配合物对耻垢分枝杆菌(M.smegmayis)有良好的抑制作用。     

N,N′-双(2-吡啶乙基)二硫代草酰胺根桥联的异三核锰(Ⅱ)铜(Ⅱ)锰(Ⅱ)、镍(Ⅱ)铜(Ⅱ)镍(Ⅱ)和三核镍(Ⅱ)配合物的合成及性质

以取代的二硫代草酰胺根作为桥联配体, 合成了3种新的三核镍配合物[Ni₃(Ped)₂](ClO₄)₂(H₂O) (1)、[Ni₃(Ped)₂](NO₃)₂(H₂O) (2)和[Ni₃(Ped)₂](Ac)₂(H₂O)₂ (3),及2种新的异三核铜镍和铜锰配合物[CuNi₂(Ped)₂](NO₃)₂(H₂O)₂ (4)和[CuMn₂(Ped)₂](NO₃)₂(H₂O)₂ (5) (H₂Ped =N,N′-双(2-吡啶乙基)二硫代草酰胺)。通过元素分析、红外光谱、紫外可见光谱、电导、电子顺磁共振谱等对配合物进行了表征，对配合物进行了热分析。测定了配合物(5)的变温磁化率，研究了配合物(5)中Cu(Ⅱ)-Mn(Ⅱ)离子间的磁相互作用，结果表明在Cu(Ⅱ)-Mn(Ⅱ)离子间的磁相互作用具有高自旋基态的非正规自旋态性质。     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)4](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}_n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)2·9H₂O}_n (5),其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构,配合物5为二维层状结构,其中金属离子由质子化的bpma配体桥连。值得注意的是,采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构,配合物3和4为螺旋链结构,配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)₄](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)₂·9H₂O}_n (5), 其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构, 配合物5为二维层状结构, 其中金属离子由质子化的bpma配体桥连。值得注意的是, 采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构, 配合物3和4为螺旋链结构, 配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

三种1,10-邻菲咯啉-铜(Ⅱ)-L-氨基酸配合物与DNA的相互作用

The Interaction of three complexes [Cu(phen)(Gly)(H₂O)]·ClO₄·2.5H₂O (1), [Cu(phen)(L-Val)(H₂O)]·ClO₄ (2) and [Cu(phen)(L-Ile)(H₂O)]·ClO₄ (3) (phen=1,10-phenanthroline, Gly=glycinate, L-Val=L-valinate, L-Ile=L-isoleucinate) with DNA have been investigated by electronic absorption spectroscopy, ethidium bromide(EB) fluorescence spectroscopy, viscosity and gel electrophoresis measurements. The intensity of maximal absorption peaks from absorption spectra are weakened with dropping DNA into the complexes. The emission intensity of EB-DNA systems in fluorescence spectroscopy have descended 50%, when the data of C_Cu / C_DNA is 30～40. Moreover, the viscosity of DNA increase and then decrease with the increasing of complexes. All of the results indicate that the interaction of complexes with DNA are partial intercalation, and the result of agarose gel electrophoresis show that the complexes can cleave pBR322 DNA in the present of H₂O₂ / vitamin C.     

三个含4，4′-(吡啶-3，5-二基)二苯甲酸配体的锌(Ⅱ)、镍(Ⅱ)和钴(Ⅱ)配位聚合物的合成、晶体结构及催化性质

采用水热方法，选用 4，4''-(吡啶-3，5-二基)二苯甲酸配体(H₂pdba)与菲咯啉(phen)、2，2''-联吡啶(bipy)或 2，2''-联咪唑(H₂biim)分别与 ZnCl₂、NiCl₂·6H₂O 和 CoCl₂·6H₂O 在 160 ℃温度下反应，合成了 2 个二维层状配位聚合物{[Zn(μ₃-pdba)(phen)]·H₂O}_n (1)和{[Ni(μ₃-pdba)(bipy)]·3H₂O}_n (2)，以及 1个具有一维链结构的配位聚合物{[Co(μ₃-pdba)(H₂biim)(H₂O)]·H₂O}_n (3)，并对其结构和催化性质进行了研究。研究表明，在70 ℃条件下配合物1在Henry反应中显示出较好的催化活性。优化了反应参数，对反应底物范围也进行了研究。     

Synthesis and characterization of three ionic pairs of Fe(II) and Co(II) complexes with tridentate salicylideneglycine

Three new transition metal complexes, [Fe^II(H₂O)₆][(C₉H₇NO₃)₂Fe^II] · H₂O (1), H[K(H₂O)₃][(C₉H₇NO₃)₂Co^II] · H₂O (2), and [Co^II(H₂O)₆][(C₉H₇NO₃)₂Co^II] · H₂O (3), with salicylideneglycine have been synthesized and characterized by elemental analysis, IR spectra, UV-Vis spectroscopy, and X-ray crystallography. The structure analyses indicate that the tridentate salicylideneglycine binds through aliphatic nitrogen, phenoxy, and carboxylic oxygen in the anion. There are many inter- and intra-molecular hydrogen bonds among lattice water, the anion, and the cation to form a 3-D network. The thermogravimetric analyses and the quantum chemistry calculations of compounds 1, 2, and 3 are also discussed.     

A three‐dimensional framework in 2,2′‐biimidazolium bis(2,2′‐biimidazole‐κ2N,N′)bis(biphenyl‐2,4′‐dicarboxylato‐κO)manganese(II) hexahydrate

In the title salt, (C₆H₈N₄)[Mn(C₁₄H₈O₄)₂(C₆H₆N₄)₂]·6H₂O, the Mn^II atom lies on an inversion centre and is coordinated by four N atoms from two 2,2′‐biimidazole (biim) ligands and two O atoms from two biphenyl‐2,4′‐dicarboxylate (bpdc) anions to give a slightly distorted octahedral coordination, while the cation lies about another inversion centre. Adjacent [Mn(bpdc)₂(biim)₂]²⁻ anions are linked via two pairs of N—H...O hydrogen bonds, leading to an infinite chain along the [100] direction. The protonated [H₂biim]²⁺ moiety acts as a charge‐compensating cation and space‐filling structural subunit. It bridges two [Mn(bpdc)₂(biim)₂]²⁻ anions through two pairs of N—H...O hydrogen bonds, constructing two R₂²(9) rings, leading to a zigzag chain in the [2] direction, which gives rise to a ruffled set of [H₂biim]²⁺[Mn(bpdc)₂(biim)₂]²⁻ moieties in the [01] plane. The water molecules give rise to a chain structure in which O—H...O hydrogen bonds generate a chain of alternating four‐ and six‐membered water–oxygen R₄²(8) and R₆⁶(12) rings, each lying about independent inversion centres giving rise to a chain along the [100] direction. Within the water chain, the (H₂O)₆ water rings are hydrogen bonded to two O atoms from two [Mn(bpdc)₂(biim)₂]²⁻ anions, giving rise to a three‐dimensional framework.     

Syntheses,crystal structures,and luminescent properties of two cadmium(II) complexes based on bis(imidazole) and dicarboxylate

Two complexes, [Cd(ip–OH)(H₂biim)(H₂O)][Cd(ip–OH)(H₂biim)(H₂O)₃]·8(H₂O) (1) and [Cd(Himdc)(H₂biim)] _n (2) (H₂ip–OH?=?5-hydroxylisophthalic acid, H₂biim?=?2,2’-biimidazolate, H₃imdc?=?4,5-imidazoledicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is a 3-D supramolecular network constructed by 0-D and 1-D motifs through hydrogen bonds and π?π interactions. Complex 2 is a 1-D zigzag polymeric coordination chain and the chains are connected to form a 3-D supramolecular network by hydrogen bonds. The complexes were characterized by elemental and thermogravimetric analyses. Fluorescence was also investigated.     

Supramolecular frameworks composed of copper(II), zinc(II), and ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different molar ratios of metal and ligand

Abstract  

Three copper(II), one zinc(II), and one ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different metal/ligand molar ratios, formulated as [Cu(3-bromo-phen)(ClO₄)(C₃H₇NO)₂(H₂O)](ClO₄) (1), [Cu(3,8-dibromo-phen)(ClO₄)(C₃H₇NO)₂(H₂O)](ClO₄) (2), [Cu(3,8-dibromo-phen)(ClO₄)(H₂O)₃](ClO₄)(H₂O)₃ (3), [Zn(3,8-dibromo-phen)₂(H₂O)₂](ClO₄)₂(H₂O)₂ (4), and [Fe(3,8-dibromo-phen)₃](ClO₄)₂(H₂O)(CH₄O)(C₃H₆O)₂ (5) (phen = 1,10-phenanthroline), have been synthesized and characterized in this paper. X-ray single-crystal diffraction studies reveal the different crystallographic symmetry and packing fashions between neighboring phen rings in 1:1 Cu(II) complexes 1–3 due to the alteration of bromo substituent 1,10-phenanthroline ligands and coordinated or free solvent molecules. Additionally, in 1:2 Zn(II) and 1:3 Fe(II) complexes 4 and 5, continuous π–π stacking and alternating π–π and dimeric p–π stacking are found.     

Hydrothermal Synthesis,Crystal Structure,and Luminescent Properties of Two Zinc(II) and Cadmium(II) 3D Metal‐­Organic Frameworks

Two zinc(II) and cadmium(II) metal‐organic frameworks with mixed ligands, {[Zn₂(biim‐4)₂(TDC)₂] · 2.5H₂O}_n ( 1 ) and {[Cd₂(biim‐4)₂(TDC)₂ · 2H₂O]}_n ( 2 ) [biim‐4 = 1,1′‐(1,4‐butanediyl)bis(imidazole); H₂TDC = thiophene‐2,5‐dicarboxylic acid], were hydrothermally synthesized. Both of them are characterized by elemental analysis, IR spectroscopy, and single crystal X‐ray diffraction. In 1 , the four‐connected Zn^II nodes are connected by four linear ligands extending into a 3D network, which further integrates a fivefold interpenetrating diamond 3D topological network and the free water molecules distribute in void space, whereas in 2 , the Cd^II ions are in a distorted octahedral arrangement linked by TDC^2– and biim‐4 ligands to construct a 3D framework. In topology analysis, C11 and C14 are simplified as 3‐connected nodes and the 3D framework displays a (3,5)‐connected net. Furthermore, the thermal and photoluminescent properties of 1 and 2 were also studied.     

Solid complexes of iron(II) and iron(III) with rutin

Solid complex compounds of Fe(II) and Fe(III) ions with rutin were obtained. On the basis of the elementary analysis and thermogravimetric investigation, the following composition of the compounds was determined: (1) FeOH(C₂₇H₂₉O₁₆)·5H₂O, (2) Fe₂OH(C₂₇H₂₇O₁₆)·9H₂O, (3) Fe(OH)₂(C₂₇H₂₉O₁₆)·8H₂O, (4) [Fe₆(OH)₂(4H₂O)(C₁₅H₇O₁₂)SO₄]·10H₂O. The coordination site in a rutin molecule was established on the basis of spectroscopic data (UV–Vis and IR). It was supposed that rutin was bound to the iron ions via 4C=O and 5C—oxygen in the case of (1) and (3). Groups 5C–OH and 4C=O as well as 3′C–OH and 4′C–OH of the ligand participate in binding metals ions in the case of (2). At an excess of iron(III) ions with regard to rutin under the synthesis conditions of (4), a side reaction of ligand oxidation occurs. In this compound, the ligands’ role plays a quinone which arose after rutin oxidation and the substitution of Fe(II) and Fe(III) ions takes place in 4C=O, 5C–OH as well as 4′C–OH, 3′C–OH ligands groups. The magnetic measurements indicated that (1) and (3) are high-spin complexes.     

Assembly of four copper(II)–2,2′-biimidazole complex-supported Strandberg-type phosphomolybdates

Four Strandberg-type phosphomolybdate-based Cu(II) complexes of 2,2′-biimidazole (C₆H₆N₄, H₂biim) and H₂O molecules, namely [Cu(H₂biim)₂(H₂O)][Cu(H₂biim)₂(HPO₄)₂(Mo₅O₁₅)]·2H₂O (1), [{Cu(H₂biim)(H₂O)}₂{μ-Cu(H₂biim)(H₂O)}(P₂Mo₅O₂₃)]₂·20H₂O (2), [Cu(H₂biim)₂][{Cu(H₂biim)(H₂O)₂}{Cu(H₂biim)₂}(HPO₄)(PO₄)(Mo₅ O₁₅)]₂·20H₂O (3), and [Cu(H₂biim)₂(H₂O)][Cu(H₂biim)₂(HPO₄)₂(Mo₅O₁₅)]·6H₂O (4) have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of a mono-supporting heteropolyoxoanion [Cu(H₂biim)₂(H₂P₂Mo₅O₂₃)]²⁻and an isolated [Cu(H₂biim)₂(H₂O)]²⁺ cation. Compound 2 is composed of two tetra-supporting heteropolyoxoanions linked via two Cu(II) complex fragments. In compound 3, there exist two symmetrical bi-supported polyoxoanion clusters and an isolated [Cu(H₂biim)₂]²⁺ fragment lying in the center of the clusters. Compound 4 is also constructed from a [Cu(H₂biim)₂(H₂P₂Mo₅O₂₃)]²⁻ polyoxoanion and a [Cu(H₂biim)₂(H₂O)]²⁺ cation, but it has a different space group and packing interactions compared with compound 1.     

Syntheses and crystal structures of copper(II) complexes derived from 2,4,6-tris(2-pyridyl)-1,3,5-triazine

Treatment of freshly precipitated Cu(OH)₂?·?xH₂O and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with oxalic and malonic acids in methanol-water at room temperature gave [Cu(tptz)(C₂O₄)(H₂O)]?·?4H₂O (1) and [Cu(pma)(C₃H₂O₄)(H₂O)]?·?H₂O (2) (pma?=?2-aminocarbonylpyridine), respectively. Reaction in the absence of any acid resulted in [Cu(bpca)(tca)]?·?2H₂O (3) (bpca?=?bis(2-pyridylcarbonyl)amide anion; tca?=?2-pyridinecarboxylate anion). Complex 1 consists of [Cu(tptz)(C₂O₄)(H₂O)] and lattice H₂O molecules; the tridentate tptz ligand, bidentate oxalate dianion and an aqua ligand are bound to Cu with distorted octahedral geometry. Complex 2 is composed of [Cu(pma)(C₃H₂O₄)(H₂O)] and lattice H₂O molecules; the bidentate 2-aminocarbonylpyridine ligand, a bidentate malonate dianion and an aqua ligand are coordinated to Cu with a slightly distorted square pyramidal geometry. Complex 3 consists of [Cu(bpca)(tca)] and lattice H₂O molecules. Square pyramidally coordinated Cu atoms are surrounded by tridentate bpca with nitrogen donor atoms and a bidentate 2-pyridinecarboxylate anion.     

1,3,5-苯三乙酸-钬配合物的合成、结构和磁性质研究

利用柔性三脚架配体1,3,5-苯三乙酸(H₃bta)与Ho(NO₃)₃•6H₂O在水热条件下组装得到了一个具有三维孔道结构的配位聚合物: {[Ho(bta)(H₂O)]•1.26H₂O}_n (1). X射线单晶衍射分析表明该配合物属三斜晶系, 空间群P-1, 晶胞参数 a＝0.7621(4) nm, b＝0.9634(4) nm, c＝1.0500(5) nm, α＝106.409(18)°, β＝105.273(18)°, γ＝100.88(2)°, Z＝2, V＝0.6839(6) nm³, D_c＝2.208 g/cm³, μ＝5.824 mm^－1, F(000)＝437, R₁＝0.0224, wR₂＝0.0462. 在1.8～300 K的温度范围内研究了该配合物固体样品的磁性质.