Tuning the topological net of two new copper(II) coordination polymers based on a paddle-wheel secondary building unit via altering the auxiliary ligands

Two new coordination polymers, [Cu(BDC)(L₁)_0.5]_n (1) and [Cu(BDC)(L₂)_0.5]_n (2) [H₂BDC=5-methyl-1,3-benzenedicarboxylic acid, L₁=1,4-bis(2-methyl-imidazol-1-yl) butane and L₂=1,4-bis(1-imidazol-yl)-2,5-dimethylbenzene], were synthesized from Cu(II), H₂BDC, and L₁/L₂. The carboxylate groups in 1 and 2 are bis-monodentate. By changing the N-donor ligands, 1 and 2 exhibit different topologies from a rob topological net to a twofold interpenetrating pcu net; however, they possess the same paddle-wheel secondary building unit in which Cu(II) has square-pyramidal geometry. The thermal stabilities of 1 and 2 are investigated.     

Construction of two new photoluminescent coordination polymers via 5-position substituted 1,3-benzenedicarboxylate

Two coordination polymers, [Cd(L1)(bib)] _n (1) and [Cd(L2)(bib)_0.5] _n (2) [H₂L1?=?5-hydroxyisophthalic acid, H₂L2?=?5-methylisophthalic acid and bib?=?1,4-bis(2-methyl-imidazol-1-yl)butane], have been synthesized and characterized by IR, elemental analysis, and X-ray diffraction. Compound 1 shows a 2-D layer structure and 2 is a two-fold interpenetrated 3-D pcu topology. The results suggest that the 5-position group affects the structure of coordination polymers. Luminescence properties of 1 and 2 are investigated.     

From discrete dinuclear to 1-D and 2-D structures: nickel dipicolinate complexes with flexible bis(imidazole) ligands

Three new complexes, [Ni₂(dpc)₂(L₁)₂(H₂O)₂]?·?4H₂O (1), [Ni(dpc)(L₂)_1.5] _n (2), and {[Ni(dpc)(L₃)_1.5]?·?2H₂O} _n (3), where H₂dpc?=?dipicolinic acid, L₁?=?1,4-bis(2-methylimidazol-1-yl)butane, L₂?=?4,4′-bis(2-methylimidazol-1-ylmethyl)biphenyl, and L₃?=?1,4-bis(benzimidazol-1-yl)-2-butylene, have been synthesized by hydrothermal methods and characterized by elemental analyses, infrared spectra, thermogravimetric analysis, and X-ray crystallography. The common structural characteristic of the three complexes is that the Ni²⁺ is coordinated by tridentate dipicolinate through nitrogen of pyridine and oxygen of carboxylate, serving as a terminal ligand. In 1, two L₁ link two [Ni(dpc)(H₂O)] units to a discrete binuclear metallomacrocycle with a 22-membered ring, which is assembled through multiple O–H?···?O hydrogen bonds to form a 3-D supramolecular framework. Complex 2 exhibits a 1-D ladder-like chain structure constructed by cis/trans-conformation L₂ linking metal centers; 3 displays a 2-D (6,3) topology, being constructed from the linking of [Ni(pdc)] by L₃. These results indicate the merits of flexible bis(imidazole) ligands as building blocks with dipicolinate for the construction of complexes with diverse structural motifs.     

3,6-二(N-咪唑/苯并咪唑基)哒嗪配体配合物的合成、结构、荧光及光催化性能

用溶剂热法设计、合成了4个金属-有机配合物[Mn(L¹)₄(OH)₂](1),{[MnL¹(H₂O)₄]SO₄}_n(2),[CdL²(NO₃)₂]_n(3)和{[Co(L²)₂](PF₆)₂}_n(4),(L¹=3,6-二(N-咪唑基)哒嗪,L²=3,6-二(N-苯并咪唑基)哒嗪),并通过元素分析、红外、X射线单晶衍射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,2为一维链结构,配合物3和4均为二维网状结构。此外,对配合物3和4的固态荧光性能及光催化的性能做了进一步研究。     

Synthesis,crystal structures,and catalytic properties of phenoxo-bridged dinuclear manganese(III) complexes with bis-Schiff bases

Two structurally similar centrosymmetric phenoxo-bridged dinuclear manganese(III) complexes, [Mn₂(L¹)₂(N₃)₂] (1) and [Mn₂(L²)₂(NCS)₂] (2), were prepared from the tetradentate bis-Schiff base ligands, N,N’-bis(salicylidene)propane-1,2-diamine (H₂L¹) and N,N’-bis(salicylidene)ethane-1,2-diamine (H₂L²), respectively, in the presence of pseudohalides. The complexes have been characterized by FTIR, elemental analyses, and molar conductivity. Structures of the complexes have been confirmed by single-crystal X-ray determination. The bis-Schiff base ligands coordinate with Mn through their phenolate oxygen and imino nitrogen. Each Mn is an octahedral. The complexes showed that they exhibit high activity in catalytic olefin oxidation.     

两个一维配位聚合物的合成、晶体结构、电化学及光学性质

合成了2个新的Robson大环配位聚合物{[Mn₂L¹(1,4-bix)₂](ClO₄)₂·5H₂O·DMF}_n(1)和{[Cu₂L²(1,4-bix)](ClO₄)₂}_n(2)(H₂L¹和H₂L²分别为1,3-丙二胺与2,6-二甲酰基-4-氟苯酚和2,6-二甲酰基-4-氯苯酚通过[2+2]缩合的产物)。2个配合物通过1,4-二(1,2,4-三唑-1-甲基)苯(1,4-bix)桥连大环单元形成一维链状结构。配合物的HOMO-LUMO能带间隙通过循环伏安法、紫外-可见漫反射光谱进行了测定,结果表明有较低的能带间隙。     

3,6-二(N-咪唑/苯并咪唑基)哒嗪配体配合物的合成、结构、荧光及光催化性能

用溶剂热法设计、合成了4个金属-有机配合物[Mn(L¹)₄(OH)₂] (1),{[MnL¹(H₂O)₄]SO₄}_n (2),[CdL²(NO₃)₂]_n (3)和{[Co(L²)₂](PF₆)₂}_n (4),(L¹=3,6-二(N-咪唑基)哒嗪,L²=3,6-二(N-苯并咪唑基)哒嗪),并通过元素分析、红外、X射线单晶衍射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,2为一维链结构,配合物3和4均为二维网状结构。此外,对配合物3和4的固态荧光性能及光催化的性能做了进一步研究。     

两个一维配位聚合物的合成、晶体结构、电化学及光学性质

合成了2个新的Robson大环配位聚合物{[Mn₂L¹（1,4-bix）₂]（ClO₄）₂·5H₂O·DMF}_n （1）和{[Cu₂L²（1,4-bix）]（ClO₄）₂}_n （2）（H₂L₁和H₂L₂分别为1,3-丙二胺与2,6-二甲酰基-4-氟苯酚和2,6-二甲酰基-4-氯苯酚通过[2+2]缩合的产物）。2个配合物通过1,4-二（1,2,4-三唑-1-甲基）苯（1,4-bix）桥连大环单元形成一维链状结构。配合物的HOMO-LUMO能带间隙通过循环伏安法、紫外-可见漫反射光谱进行了测定,结果表明有较低的能带间隙。     

Synthesis and characterization of three heptaaza manganese(II) macrocyclic Schiff base complexes containing two 2-pyridylmethyl pendant arms

Three new Mn(II) bis(pendant arm)-macrocyclic Schiff base complexes, [MnLⁿ]²⁺(n = 1, 2, 3), have been prepared via cyclocondensation of 2,6-diacetylpyridine with three different branched hexadentate amines (3,6-bis(2-pyridylmethyl)-3,6-diazaoctane-1,8-diamine (1), 3,7-bis(2-pyridylmethyl)-3,7-diazanonane-1,9-diamine (2) and 3,8-bis(2-pyridylmethyl)-3,8-diazadecane-1,10-diamine (3)) in the presence of MnCl₂ in methanol. The ligands, L, are 15-, 16- and 17-membered pentaaza macrocycles having two 2-pyridylmethyl pendant arms [L¹; 2,13-dimethyl-6,9-bis(2-pyridylmethyl)-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18), 2, 12, 14, 16-pentaene, L²; 2,14-dimethyl-6,10- bis(2-pyridylmethyl)-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19), 2, 13, 15, 17-pentaene and L³; 2,15-dimethyl-6,11-bis(2-pyridylmethyl)-3,6,11,14,20-pentaazabicyclo[14.3.1]eicosa-1(20),2,14,16,18-pentaene]. All the complexes have been characterized by physicochemical and spectroscopic methods. The crystal structure of [MnL¹](ClO₄)₂·CH₃CN has been determined and indicates that in the solid state, the complex adopts a slightly distorted pentagonal bipyramidal geometry with the Mn(II) centre located within a pentaaza macrocycle with two 2-pyridylmethyl pendants coordinating in the axial positions.     

Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2Mo2(CO)4(μ,η2-As2)], AgI Salts and N-Donor Organic Molecules

The reaction of the organometallic diarsene complex [Cp₂Mo₂(CO)₄(η²-As₂)] ( 1 ) with Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]) yielded the Ag^I monomer [Ag(η²- 1 )₃][TEF] ( 2 ). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic–organic hybrid assemblies upon its reaction with N-donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2′-bipyrimidine ( L1 ) yielded the dicationic molecular compound [{(η²- 1 )₂Ag}₂(μ- L1 )][TEF]₂ ( 3 ) or the 1D polymer [{(η²- 1 )Ag}(μ- L1 )]_n[TEF]_n ( 4 ) depending on the ratio of the reactants. However, its reactions with the pyridine-based linkers 4,4′-bipyridine ( L2 ), 1,2-bis(4-pyridyl)ethylene ( L3 ) and 1,2-bis(4-pyridyl)ethyne ( L4 ) allowed the formation of the 2D polymers [{(η²- 1 )Ag}₂(μ- Lx )₃]_n[TEF]_2n [ Lx=L2 ( 5 ), L3 ( 6 ), L4 ( 7 ), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1 , [Ag(CH₃CN)₃][Al{OC(CF₃)₂(CCl₃)}₄] ([Ag(CH₃CN)₃][TEF^Cl]) and linkers L2 – L4 to produce the 2D polymers [{(η²- 1 )Ag}₂(μ, Lx )₃]_n[TEF^Cl]_2n [ Lx = L2 ( 8 ), L3 ( 9 ), L4 ( 10 ), respectively].     

Syntheses,structures, and photoluminescence of three cadmium(II) coordination polymers with flexible bis(benzimidazole) ligands

Three cadmium(II) coordination polymers, [CdBr₂(L₁)] _n (1), [CdI₂(L₂)] _n (2), and Cd₂Br₄(L₃)₂ (3), where L₁?=?1,3-bis(5,6-dimethylbenzimidazole)propane, L₂?=?1,4-bis(5,6-dimethylbenzimidazole)butane, and L₃?=?1,6-bis(5,6-dimethylbenzimidazole)hexane, have been synthesized by hydrothermal methods and characterized by elemental analyses, IR spectra, TGA, PXRD, and X-ray crystallographic diffraction. Complex 1 contains a 1-D helical chain in which CdBr₂ units are linked by L₁. For 2, each CdI₂ is connected by two different conformations of L₂ to form a 1-D zigzag chain. For 3, each CdBr₂ is linked by L₃ bridges to afford a binuclear structure. These results indicate that the spacer length of the ligands play important roles in assembly of Cd(II) coordination polymers. Thermogravimetric analyses and solid-state luminescent properties of the complexes have also been investigated.     

Two copper(II) metal–organic networks derived from bis-pyridyl-bis-amide ligands and aromatic polycarboxylates: a 2-D layered structure and a 4-connected trinodal 3-D topology

Two metal–organic coordination polymers, [Cu₃(4-bpcb)₂(1,2,4-btc)₂(H₂O)₂] (1) and [Cu₃(3-bpcb)₃(btec)_1.5] (2), have been synthesized from hydrothermal reaction of copper chloride with mixed ligands [4-bpcb?=?N,N′-bis(4-pyridinecarboxamide)-1,4-benzene, 3-bpcb?=?N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, 1,2,4-H₃btc?=?1,2,4-benzenetricarboxylic acid, and H₄btec?=?1,2,4,5-benzenetetracarboxylic acid]. X-ray diffraction analysis reveals that 1 exhibits a 2-D layer structure and 2 possesses a three-dimensional (3-D) network. In 1 and 2, Cu^II ions are connected by bridging 1,2,4-btc or btec to form 2-D polymeric layers. Cu-1,2,4-btc layer does not propagate into a 3-D coordination framework in 1 due to 4-bpcb showing monodentate coordination (via ligation of only one pyridyl nitrogen). In 2, Cu-btec 2-D layers are further extended into a 3-D network with (6⁴.8²)₃ topology by 3-bpcb ligand in μ ₂-bridging coordination (via ligation of two pyridyl nitrogens). The different structures of the two complexes illustrate the influence of different polycarboxylates and N-donor positions of organic ligands on the formation of such coordination architectures. Moreover, the thermal properties and electrochemical properties of the copper complexes bulk-modified carbon paste electrodes have been studied.     

基于三羧酸构筑的两个金属-有机骨架(MOFs):合成,晶体结构和性质(英文)

以1,3-二(4′-羧基苯氧基)苯甲酸(H3L)为配体与金属盐反应,在水热条件下成功合成了2个金属-有机骨架(MOFs),分别为[Cd2(CH3COO)(L)(H2O)2]n(1)和[Na(H2L)]n(2)。由于H3L配体配位模式的不同,配合物表现出不同的网络结构。单晶结构分析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,C2/c空间群。配合物1中Cd2+离子的次级构筑单元经由L3-连接形成三维网络结构。配合物2是一个5-连接的拓扑网络结构,其拓扑符号为(46·64)。此外,还对配合物1的荧光性能进行了分析。     

Copper(I) and copper(II) complexes with pyrazine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide

Four copper(II) complexes and one copper(I) complex with pyridine-containing pyridylalkylamide ligands N-(pyridin-2-ylmethyl)pyrazine-2-carboxamide (HL^pz) and N-(2-(pyridin-2-yl)ethyl)pyrazine-2-carboxamide (HL^pz?) were synthesized and characterized. The X-ray crystal structures of [Cu₂(L^pz)₂(4,4?-bipy)(OTf)₂] (1, OTf?=?trifluoromethanesulfonate, 4,4?-bipy?=?4,4?-bipyridine) and [Cu(L^pz)(py)₂]OTf·H₂O (2, py?=?pyridine) revealed binuclear and mononuclear molecular species, respectively, while [Cu(L^pz)(μ₂-1,1-N₃)]_n (3), [Cu(L^pz?)(μ₂-1,3-N₃)]_n (4), and [Cu(HL^pz)Cl]_n (5) are coordination polymer 1-D chains in the solid state.     

基于三羧酸构筑的两个金属-有机骨架(MOFs):合成,晶体结构和性

以1,3-二(4'-羧基苯氧基)苯甲酸(H₃L)为配体与金属盐反应,在水热条件下成功合成了2个金属-有机骨架(MOFs),分别为[Cd₂(CH₃COO)(L)(H₂O)₂]_n (1)和[Na(H₂L)]_n (2).由于H₃L配体配位模式的不同,配合物表现出不同的网络结构.单晶结构分析表明,配合物1属于三斜晶系,P1 空间群,配合物2属于单斜晶系,C2/c空间群.配合物1中Cd₂₊离子的次级构筑单元经由L^3-连接形成三维网络结构.配合物2是一个5-连接的拓扑网络结构,其拓扑符号为(4⁶·6⁴).此外,还对配合物1的荧光性能进行了分析.     

Coordination polymers with adamantanediacetate bridges: syntheses, structures, and magnetic properties

Abstract  Two new coordination polymers, [CoL(bpp)] _n (1) and [MnL(bipy)] _n ·0.25nH₂L·0.5nH₂O (2) (H₂L = 1,3-adamantanediacetic acid, bpp = 1,3-bis(4-pyridyl)propane, bipy = 4,4′-bipyridine), were synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, and thermal analysis. Complex 1 is an one-dimensional (1D) chain structure of Co(II) bridged by L²⁻ as well as bpp. Complex 2 consists of a two-dimensional (2D) (3,6)-connected topology layer structure. Variable temperature magnetic susceptibility measurements in the range of 2–300 K reveal the existence of weak antiferromagnetic interactions in two complexes with J = −1.74 cm⁻¹, g = 2.26 for 1 and J = −0.10 cm⁻¹, g = 1.67 for 2. Index abstract  Two mental-organic frameworks, namely [CoL(bpp)] _n (1) and [MnL(bipy)] _n ·0.25nH₂L·0.5nH₂O (2) (H₂L = 1,3-adamantanediacetic acid, bpp = 1,3-bis(4-pyridyl)propane, bipy = 4,4′-bipyridine), have been synthesized based on 1,3-adamantanediacetic acid and N-donor coligand with metal ions Co(II) and Mn(II). The magnetic measurement of the two polymers reveals typical antiferromagnetism exchange. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,structures, catalytic,and anticancer activities of some coordination compounds involving two new triazole derivatives

Five N-heterocyclic carboxylate-based coordination complexes, [Co(L¹)₂(H₂O)₂]·2H₂O (1), [Cd(L¹)₂(H₂O)₂]·2H₂O (2), [Co(L²)(H₂O)₃] (3), [Ni(L²)(H₂O)₃] (4), and [Cu₂(L²)₂(H₂O)₂] (5), have been synthesized and characterized by elemental analysis, IR spectroscopy, Powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray crystallography, where HL¹ is 2-((5-amino-1H-1,2,4-triazol-3-yl)thio)acetic acid and H₂L² is 2-((5-amino-1-(carboxymethyl)-1H-1,2,4-triazol-3-yl)thio)acetic acid. In these complexes, the hydrogen bonds (H-bonds) play an important role in their packing structures. Complex 1 has nine H-bonds showing a 3-D sqc38 topology. Complex 2 has 17 H-bonds exhibiting a 3-D hxl network. Complexes 3 and 4 are isomorphic, both of which possess ten H-bonds to present a 3-D btc topology. Complex 5 with eight H-bonds forms a 2-D sq1 structure. In addition, complex 3 catalyzes the decolorization of methyl orange. Meanwhile, 1, 3, and 5 show certain anticancer activities to inhibit the growth of HepG2 cells.     

Tuning the bridging modes of Cu-azido complexes with Schiff bases by varying the terminal groups

Three azido-bridged copper(II) complexes, [Cu₂(L¹)₂(μ_1,1,3-N₃)₂] _n ·2nH₂O (1), [Cu₄(L²)₄(μ_1,1-N₃)₂(μ_1,1,3-N₃)₂] _n (2), and [Cu₂(L³)₂(μ_1,1-N₃)₂] (3), where L¹, L², and L³ are the deprotonated forms of 4-bromo-2-[(2-methylaminoethylimino)methyl]phenol (HL¹), 4-bromo-2-[(2-ethylaminoethylimino)methyl]phenol (HL²), and 4-bromo-2-[(2-isopropylaminoethylimino)methyl]phenol (HL³), respectively, have been prepared and structurally characterized by single-crystal X-ray diffraction analysis and IR spectra. The slight differences in the terminal groups of the Schiff bases lead to different bridging modes of the azido groups.     

A bi-chain CoII coordination framework bridged by water molecules: magnetic properties and photocatalytic behavior

A new coordination framework, [Co₂(L)₂(bpy)₂(H₂O)]_n (1) (H₂L = (4-phenyl)-2,6-bis(4-carboxyphenyl)pyridine and bpy = 2,2′-bipyridine), has been prepared and structurally characterized. Complex 1 shows an interesting bi-chain substructure bridged by coordinated water molecules, which is further extended into a three-dimensional (3-D) supramolecular structure by π–π stacking interactions. Moreover, the magnetic properties and photocatalytic activity for degradation of methyl orange have been investigated.     

Zinc(II) complexes containing N′-aromatic group substituted N,N′,N-bis((1H-pyrazol-1-yl)methyl)amines: Synthesis,characterization, and polymerizations of methyl methacrylate and rac-lactide

A novel series of Zn(II) complexes [L_nZnCl₂] (L_n = L_A ? L_F) based on N,N′,N-bis((1H-pyrazol-1-yl)methyl)amine bidentate ligands, N,N-bis((1H-pyrazol-1-yl)methyl)-3,5-dimethylaniline [L_A], N,N-bis((1H-pyrazol-1-yl)methyl)-2,6-dimethylaniline [L_B], N,N-bis((1H-pyrazol-1-yl)methyl)-2,6-diethylaniline [L_C], N,N-bis((1H-pyrazol-1-yl)methyl)-2,6-diisopropylaniline [L_D], N,N-bis((1H-pyrazol-1-yl)methyl)-4-bromoaniline [L_E] and N,N-bis((1H-pyrazol-1-yl)methyl)benzhydrylamine [L_F], has been synthesized and characterized. X-ray structures of these Zn(II) complexes showed a distorted tetrahedral geometry. No interaction exists between the N_amine and the Zn(II) center in the [L_nZnCl₂] (L_n = L_A ? L_F) complexes, resulting in formation of an eight-membered chelate ring. [L_FZnCl₂] exhibited the highest catalytic activity (3.95 × 10⁴ g PMMA/mol·Zn·h) for the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) at 60 °C and yielded high molecular weight (M_w) (11.0 × 10⁵ g/mol) of poly(methylmethacrylate) (PMMA). All the complexes resulted in syndiotactic enriched PMMA with high T_g (125–131 °C). The steric bulk of ligand architecture plays an influential role in controlling the catalytic activity and stereoregularity of the resultant PMMA. Further, alkyl derivatives [L_nZnMe₂] (L_n = L_A ? L_F) of synthesized Zn(II) complexes, generated in situ, showed moderate to high activities toward ring opening polymerization (ROP) of rac-lactide (rac-LA) and yielded heterotactic polylactide (PLA) with P_r up to 0.95 at ?50 °C. The activity and stereoselectivity toward ROP of rac-LA by these dimethyl Zn(II) complexes should be considered as a combined effect of steric hindrance and electronic density around the metal center.