3-(2-吡啶基)-1,2,4-三唑配体Co(Ⅱ)Cu(Ⅱ)和Cd(Ⅱ)配合物的合成、结构及荧光性质

利用3-（2-吡啶基）-1,2,4-三唑配体（HL）和不同的金属盐设计合成了5个配合物[Co（HL）₂（H₂O）₂]（NO₃）₂（1）、[Cu₂（L）₂（NO₃）₂（H₂O）₄]（2）、[Cu₂（L）₂（AcO）₂（H₂O）₂]·6H₂O（3）、[Cu₂（L）₂（HL）₂（ClO₄）₂]·2CH₃CN（4）和[Cd₂（L）₂（HL）₂（NO₃）₂]·2H₂O（5）,并通过X射线单晶衍射、红外、元素分析、X射线粉末衍射和热重对配合物结构进行了表征。测试结果表明配合物1具有单核结构,并且可以通过氢键的相互作用形成二维超分子结构。配合物2~5为双核结构。配合物2和5可以通过氢键的相互作用形成二维超分子结构。配合物3通过氢键的相互作用形成三维超分子结构。研究了配合物中HL配体的配位模式。此外,研究了配体HL和配合物2和5的固态荧光性质及荧光寿命。     

4-吡啶-NH-1,2,3-三唑构筑的两个Zn(II)配合物的合成、结构和荧光性质

以4-吡啶-NH-1,2,3-三唑（L）为配体与ZnCl₂·H₂O分别在溶剂热和室温挥发条件下得到了配合物[Zn₂（L）₂Cl₄]（1）和[Zn（L）₂ Cl₂]·2H₂O（2）,并进行了红外、元素分析、单晶衍射、粉末衍射等表征。2个配合物中,超分子相互作用对于配合物的结构有很大影响。其中,配合物1由氢键和π-π相互作用形成3D堆积结构,配合物2通过氢键作用形成堆积结构。同时,在常温下研究了配体以及2个配合物的固体和液体荧光性质。     

3-乙基-2-乙酰吡嗪缩N(4)-(对甲苯)氨基硫脲Ga(Ⅲ)、In(Ⅲ)配合物的合成、晶体结构和DNA结合性质

以3-乙基-2-乙酰吡嗪N（4）-（对甲苯）氨基硫脲（HL）为原料,合成了[Ga（L）₂]NO₃·4CH₃OH（1）和[In（L）₂]NO₃·1.75CH₃OH（2）两种新型配合物,并进行了X射线衍射分析表征。结果表明,配合物1和配合物2同构但具有不同数目的结晶甲醇分子。每个配合物的金属中心被2个拥有[N₂S]供体的配体阴离子包围,采取扭曲的八面体配位几何。此外,荧光光谱表明配合物与DNA的相互作用强于配体。     

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。     

4-吡啶-NH-1,2,3-三唑构筑的两个Zn（Ⅱ）配合物的合成、结构和荧光性质

以4-吡啶-NH-1,2,3-三唑（L）为配体与ZnCl₂·H₂O分别在溶剂热和室温挥发条件下得到了配合物[Zn₂（L）₂Cl₄]（1）和[Zn（L）₂ Cl₂]·2H₂O（2）,并进行了红外、元素分析、单晶衍射、粉末衍射等表征。2个配合物中,超分子相互作用对于配合物的结构有很大影响。其中,配合物1由氢键和π-π相互作用形成3D堆积结构,配合物2通过氢键作用形成堆积结构。同时,在常温下研究了配体以及2个配合物的固体和液体荧光性质。     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构

利用3,5-二（3-吡啶）-4-氨基-1,2,4-三唑（L）配体与Co（Ⅱ）/Cu（Ⅱ）盐室温下反应得到了一维的配位聚合物{[CoL（H₂O）₄]SO₄·H₂O}_n（1）和单核配合物[Cu（hfac）₂L₂]（2,hfac=hexafluoroacetylacetonate）。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co（Ⅱ）离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu（Ⅱ）离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构

利用3,5-二（3-吡啶）-4-氨基-1,2,4-三唑（L）配体与Co（Ⅱ）/Cu（Ⅱ）盐室温下反应得到了一维的配位聚合物{[CoL（H₂O）₄]SO₄·H₂O}_n（1）和单核配合物[Cu（hfac）₂L₂]（2,hfac=hexafluoroacetylacetonate）。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co（Ⅱ）离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu（Ⅱ）离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

三个含2,4-二氯苯乙酸配体的Mg(Ⅱ)、Ca(Ⅱ)和Cd(Ⅱ)配合物的合成及晶体结构

以2,4-二氯苯乙酸、4,4''-联吡啶分别和硫酸镁、氯化钙和硝酸镉反应,采用自然挥发法制备了3个配合物[Mg（DCBA）₂（H₂O）₄]·3（4,4''-bipy）（1）、[Ca（DCBA）（H₂O）₄]·DCBA·H₂O（2）和[Cd（DCBA）₂（H₂O）₂]·2H₂O（3）（DCBA=2,4-二氯苯乙酸,4,4''-bipy=4,4''-联吡啶）,并对其进行了元素分析、红外光谱、热稳定性和X射线单晶衍射的表征,研究了配合物3的荧光性质。结果表明,配合物1、2和3均为零维结构,其中,配合物1中存在O-H…O、O-H…N、C-H…O、C-H…Cl和O-H…π氢键作用,而配合物2和3中存在O-H…O和C-H…Cl氢键作用,并以此分别形成了3D超分子结构。     

三个含2,4-二氯苯乙酸配体的Mg(Ⅱ)、Ca(Ⅱ)和Cd(Ⅱ)配合物的合成及晶体结构

以2,4-二氯苯乙酸、4,4''-联吡啶分别和硫酸镁、氯化钙和硝酸镉反应,采用自然挥发法制备了3个配合物[Mg（DCBA）₂（H₂O）₄]·3（4,4''-bipy）（1）、[Ca（DCBA）（H₂O）₄]·DCBA·H₂O（2）和[Cd（DCBA）₂（H₂O）₂]·2H₂O（3）（DCBA=2,4-二氯苯乙酸,4,4''-bipy=4,4''-联吡啶）,并对其进行了元素分析、红外光谱、热稳定性和X射线单晶衍射的表征,研究了配合物3的荧光性质。结果表明,配合物1、2和3均为零维结构,其中,配合物1中存在O-H…O、O-H…N、C-H…O、C-H…Cl和O-H…π氢键作用,而配合物2和3中存在O-H…O和C-H…Cl氢键作用,并以此分别形成了3D超分子结构。     

含吡嗪的缩氨基脲配体Ni(Ⅱ)/Cd(Ⅱ)配合物的晶体结构及与DNA的相互作用

合成配合物[NiL₂]·CH₃OH·0.5H₂O（1）和[Cd（HL）Cl₂]（2）（HL=3-甲基2-乙酰吡嗪缩4-苯基氨基脲）并通过单晶衍射、元素分析及红外光谱表征其结构。单晶衍射结果表明,配合物1中,Ni（Ⅱ）离子与2个拥有N₂O电子供体的阴离子配体L^-配位,配位构型为扭曲的八面体。而配合物2中,Cd（Ⅱ）离子与1个中性三齿配体HL和2个氯离子配位,拥有扭曲的四方锥配位构型。荧光光谱结果表明,配合物与DNA的相互作用强于配体。     

Syntheses,structural characterization,and properties of Mn(II) and Cd(II) complexes from 5-[4-(1H-imidazol-1-Yl)phenyl]-1H-tetrazole

Reactions of Mn(II) and Cd(II) salts with 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazole (HL) under hydrothermal conditions result in complexes [Mn(L)₂(H₂O)₄] · 2H₂O (I) and [Cd(L)₂(H₂O)₂] (II), which have been characterized by single crystal and powder X-ray diffractions (CIF files CCDC nos. 943861 (I), 943862 (II)), IR spectroscopy, element and thermogravimetric analyses. Two complexes exhibit structural diversity dependent on different metal salts. Complex I shows discrete mononuclear structure, which can be further linked to build a 3D supramolecular framework through hydrogen bonding interactions. Complex II displays 1D zigzag-chain structure, and an extended 3D framework can be formed by hydrogen bonding. Interestingly, tetranuclear water clusters were generated in I, which can be linked by Mn²⁺ ions to show 1D metal-bridged water cluster-chain structure. The present work provides an example that metal centers impact on coordination modes of ligand and consequent structural variation of resulted complexes. Moreover, fluorescence property of II was investigated.

     

Syntheses,crystal structures and antibacterial activities of M(II) benzene-1,2,3-triyltris(oxy)triacetic acid complexes

Four metal(II) complexes with benzene-1,2,3-triyltris(oxy)triacetic acid (H₃L), {[Co_1.5(L)(H₂O)₆]·6H₂O}_n (1), {[Co_1.5(L)(4,4′-bipy)_1.5(H₂O)₄]·4H₂O}_n (2), {[Co(HL)(2,2′-bipy)(H₂O)₂]·1.5H₂O}_n (3), and {[Cu(HL)(phen)(H₂O)₂]·H₂O}_n (4) (4,4′-bipy = 4,4′-bipyridine; 2,2′-bipy = 2,2′-bipyridine; phen = phenanthroline), were prepared and structurally characterized. Complex 2 displays a 1-D structure, while 1, 3, and 4 reveal 0-D structures, which further extend to 3-D supramolecular networks by hydrogen bonding interactions, of which 1 and 4 contain double-helical chains, 2 includes meso-helices, and 3 comprises single-helices. Furthermore, the thermal stabilities and antibacterial activities of the complexes were studied.     

Synthesis,structure and luminescent properties of Cd(II) and Zn(II) complexes constructed from 3,5-dimethyl-2, 6-pyrazinedicarboxylic acid

[Cd₂(phen)₂(DPZDA)₂(H₂O)₂] · 8H₂O (1) and [Zn(phen)(DPZDA)(H₂O)] · 2H₂O (2) have been synthesized by reaction of Cd(NO₃)₂/Zn(NO₃)₂ with phen and DPZDA (where phen = 1,10-phenanthroline, H₂DPZDA = 3,5-dimethyl-2,6-pyrazinedicarboxylic acid) in aqueous ethanol solution. Elemental analysis, IR spectra, thermal analyses and X-ray single crystal diffraction were carried out to determine the composition and crystal structure of 1 and 2. In 1, a 2D supramolecular network containing a novel metal-water decamer were formed by hydrogen bonds. In 2, a 2D supramolecular structure was constructed from hydrogen bonds and π·· · π interactions. Moreover, 1 and 2 displayed photoluminescent properties in the blue range at room temperature.     

Five new cobalt(II) complexes based on indazole derivatives: synthesis,DNA binding and molecular docking study

Five cobalt(II) complexes based on 1H-indazole-3-carboxylic acid (H₂L), [Co(phen)(HL)₂]·2H₂O (1), [Co(5,5′-dimethyl-2,2′-bipy)(HL)₂] (2), [Co(2,2′-bipy)₂(HL)₂]·5H₂O (3), [Co₂(2,9-dimethyl-1,10-phen)₂(L)₂] (4) and [Co₂(6,6′-dimethyl-2,2′-bipy)₂(L)₂]·H₂O (5) (2,2'-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and structurally characterized by elemental analyses, IR and UV-vis spectroscopies and single-crystal X-ray crystallography. The results indicate that 1–3 possess mononuclear Co(II) structures, while 4 and 5 exhibit binuclear structure. 1D water tape which is linked by the multiple hydrogen bonds was embedded in the 3D motif of complex 3. Complexes 4 and 5 show two orthogonal planes of motif that was constituted by phen/2,2′-bipy and indazole acid, respectively. The intermolecular interactions including hydrogen bonding and π-π stacking interactions are stabilizing these complexes. The interactions of the synthesized complexes with calf-thymus DNA (CT-DNA) have been investigated by UV-vis absorption titration, ethidium bromide displacement assay and viscosity measurements. The results reveal that the complexes could interact with CT-DNA via a groove binding mode. Their behavior rationalization was further theoretically studied by molecular docking.     

Synthesis,structural studies,and antibacterial activity of zinc,copper, and silver complexes derived from N′-(1-(pyrazin-2-yl)ethylidene)isonicotinohydrazide

The multidentate Schiff-base ligand N′-(1-(pyrazin-2-yl)ethylidene)isonicotinohydrazide (HL) has been prepared. Reaction with zinc, copper, and silver nitrate afford three complexes, [Zn(HL′)₂](NO₃)₂·3H₂O (1), {[Cu₂(L)₂(NO₃)(H₂O)₂]·NO₃}_n (2) and {[Ag₂(L)₂]·3H₂O}_n (3). These complexes have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. In 1, HL is a neutral tridentate ligand, whereas in 2 and 3, HL is a deprotonated tetradentate ligand. The hydrogen bonding interactions between NO₃^? and the host framework result in various supramolecular polymeric structures: a 2-D layer for 1 and 3-D network for 2 and 3. The antibacterial activities of these complexes have been investigated and the results indicate that 3 showed good antibacterial activities.     

Syntheses and crystal structures of phthalato-, succinato-, maleato-, acetylenedicarboxylato-bridged [bis(2-pyridylcarbonyl)amide]copper(II) complexes

Self-assemblies of the 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and Cu(OH)₂ in the presence of dicarboxylate ligands yielded four new complexes, [Cu₄(bpca)₄(L1)₂(H₂O)₂]·5H₂O (1), [Cu₂(bpca)₂(L2)(H₂O)₂]·2H₂O (2), [Cu₂(bpca)₂(L3)(H₂O)₂]·H₂O (3), and [Cu₂(bpca)₂(L4)(H₂O)₂]·3H₂O (4) (bpca = bis(2-pyridylcarbonyl)amide anion, H₂L1 = phthalic acid, H₂L2 = succinic acid, H₂L3 = maleic acid, H₂L4 = acetylenedicarboxylic acid). Their structures were determined by single-crystal X-ray diffraction analyzes and further characterized by IR spectra and thermogravimetric analyzes. The five-coordinate Cu ions in 1 are bridged by phthalate to form 1-D chains, which are assembled into 3-D frameworks by extensive hydrogen bonds. Compounds 2–4 possess similar structures, built up of [Cu₂(bpca)₂(L)(H₂O)₂] (L = L2 for 2, L3 for 3, L4 for 4) and lattice molecules. The 3-D frameworks of 2–4 are completed by hydrogen bond interactions.     

1,2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质

通过配体1,2-环己二胺缩邻香兰素（H₂L）和不同的镱盐反应,合成了4个镱稀土配合物[Yb（H₂L）₂]（ClO₄）₃·2CH₃OH·H₂O（1）,[Yb₄（L）₄（NO₃）₂（H₂O）₂]（PF₆）₂·4CH₃CN（2）,[Yb₄（L）₄（H₂O）₂Cl₂]（PF₆）₂·2CH₂Cl₂·2H₂O（3）和[Yb₄（L）₄（NO₃）₂（H₂O）₂][Yb（NO₃）₃（H₂O）₂（CH₃OH）]（NO₃）₂ ·4CH₂Cl₂·6CH₃OH（4）。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

Supramolecular complexes constructed with carboxylate Cu(II) and 2-(2-pyridyl)-benzimidazole via hydrogen bonding

Four copper(II) supramolecular complexes, {[Cu(Hpb)(mal)]·H₂O} _n (1), (Hpb?=?2-(2-pyridyl)-benzimidazole, mal?=?maleate), [Cu₄(pb)₄(cro)₄(MeOH)₂]·2MeOH (2) (cro?=?crotonate), [Cu₂(pb)(Hpb)(mac)₃(MeOH)] (3) (mac?=?α-methacrylate) and [Cu(Hpb)(acr)₂(H₂O)] (4) (acr?=?acrylate), based on carboxylate copper(II)-aromatic ligand systems which are assembled by combination of metal coordination, hydrogen-bond and π–π interactions, have been rationally designed and synthesized. Complex 1 forms a 3D supramolecular network with open channels by extending 2D undulating sheets constructed from 1D helical chains. Complex 2 generates a 2D grid-like sheet via unusual finite-chain tetranuclear molecules, with four copper atoms arranged in a line; the unit does not extend further due to the capping effect of the terminal methanol. Complexes 3 and 4 present a 1D sinusoidal structure and a 3D columnar network with 1D ladder-shaped double chains, respectively. Interestingly, coligand Hpb, deprotonated or/and neutral in different supramolecular complexes, provides hydrogen bonding and π–π stacking interactions. In complexes 2, 3 and 4, carboxylate anions show various bridging modes, which are reflected in their magnetic properties. Weak ferromagnetic coupling (syn-anti µ-OCO) exists in 1, antiferromagnetic (syn-syn µ-OCO) and weak ferromagnetic coupling (µ-O of the??COO group) in 2 and antiferromagnetic coupling (syn-syn µ-OCO) in 3.     

U(VI) and Zn(II) coordination complexes with 5-[N-acetato(4-pyridyl)]tetrazolate anions

A U(VI) mononuclear coordination complex [UO₂(a4-ptz)₂·(H₂O)₃] (1) and a Zn(II) 1-D coordination polymer [Zn(a4-ptz)₂·(H₂O)₂]·2H₂O (2) have been synthesized with 5-[N-acetato(4-pyridyl)]tetrazolate (a4-ptz) as ligand. Complex 1 has a slightly distorted pentagonal bipyramid around each U center. Complex 2 is octahedral with four a4-ptz and two water ligands. Each Zn center is linked by carboxylate-O(1) and tetrazolate-N(2) of a4-ptz forming a 1-D polymeric chain. Complexes 1 and 2 are self-assembled to form 3-D supramolecular structures through hydrogen bonds. The luminescence properties of 1 and 2 were investigated at room temperature in the solid state. The results suggest that 1 and 2 may be useful as photoactive materials.