过渡金属氨基酸席夫碱配合物的合成

合成了6个过渡金属氨基酸席夫碱配合物——L-酪氨酸缩水杨醛合铬(钼),L-赖氨酸缩水杨醛合铬(钼),DL-α-丙氨酸缩水杨醛合铬(钼),其结构经UV,IR和元素分析表征。UV测定结果表明,配合物均可与DNA发生插入作用。     

Syntheses,Characterization, and Crystal Structures of a Dinuclear Complex and Coordination Polymer of Mercury(II) with Schiff Base Ligands containing N3 and N4 Donors

Two dinuclear mercury(II) iodide compounds, [Hg₂(L)(I)₄] ( 1 ) and [(L′)Hg(μ‐I)₂HgI₂]_n ( 2 ) [L = N,N′‐bis(phenyl(pyridin‐2‐yl)methylene)propane‐1,2‐diamine and L′ = N‐(phenyl(pyridin‐2‐yl)methylene)propane‐1,2‐diamine] were synthesized and characterized. The molecular structures of [Hg₂(L)(I)₄] ( 1 ) and [(L′)Hg(μ‐I)₂HgI₂]_n ( 2 ), which were determined by single‐crystal X‐ray diffraction, indicate that each Hg^II in 1 has a distorted tetrahedral environment around the metal atom with a HgN₂I₂ chromophore, whereas in 2 one mercury(II) atom adopts a distorted tetrahedral arrangement with a HgI₄ chromophore and the other has a distorted square pyramidal environment with HgN₃I₂ chromophore. In the solid state, compound 2 consists of a 1D coordination polymer structure.     

One New Schiff Base Complex with One in Situ Synthesized Ligand： Synthesis and Structure

1 INTRODUCTION The transition-metal Schiff base complexes have attracted much attention due to their beautiful struc- tures, multifunctions like catalysis[1～3] and materials science[4～6]. Recently, some Schiff base complexes based on guanidinate ligands have been explored[7～9], and most of them were synthesized by stepwise reactions. Due to the steric and electrical flexibility and abundant donor functionality of the guanidinate species, the ligand may adopt various coordination modes.…     

一个具有铁电性质的手性西佛碱

1,1,1,5,5,5-六氟戊烷-2,4-二酮和(1S,2S)-(--)-1,2-环己二胺反应可得到一个手性西佛碱 (1Z,4Z)-2,4-二（三氟甲基)-5a,6,7,8,9,9a-六氢-3H-benzo[b][1,4]diazepine (1).荧光分析表明当激发光波长为437 nm时,化合物发射波长在488 nm。晶体学分析该化合物属于具有铁电行为的非中心空间群C2,实验得到的铁电电滞回线证实了这个西佛碱具有典型的铁电性,剩余极化强度为0.01 μC/cm2,矫顽场强为0.27 kV/cm。     

邻氨基苯酚Schiff碱多核配合物的合成与表征

合成了3-羧基水杨醛缩邻氨基苯酚Sch iff碱及其三核铜,三核镍配合物.用质谱分析,核磁共振,红外光谱,元素分析对配体和配合物的结构进行了表征.磁性研究表明,这两种配合物的金属离子间均存在着较强的反铁磁性自旋交换相互作用.     

Synthesis,Structure, and Magnetic Properties of a Series of Dinuclear Lanthanide Complexes Assembled by Acetate and a Schiff Base Ligand

Five dinuclear lanthanide complexes [Ln₂L₂(NO₃)₂(OAc)₄] · 2CH₃CN [Ln = Gd ( 1 ), Tb ( 2 ), Dy ( 3 ), Ho ( 4 ), and Er ( 5 )] [L = 2‐((2‐pyridinylmethylene)hydrazine)ethanol] were synthesized from the reactions of Ln(NO₃)₃ · 6H₂O with L and CH₃COOH in the presence of triethylamine. Their crystal structures were determined. They show similar dinuclear cores with the two lanthanide ions bridged by four acetate ligands in the μ₂‐η¹:η² and μ₂‐η¹:η¹ bridging modes. Each Ln^III ion in complexes 1 – 5 is further chelated by one L ligand and one nitrate ion, leading to the formation of a nine‐coordinated mono‐capped square antiprism arrangement. The dinuclear molecules in 1 – 5 are consolidated by hydrogen bonds and π ··· π stacking interactions to build a two‐dimensional sheet. Their magnetic properties were investigated. It revealed antiferromagnetic interactions between the Gd^III ions in 1 and ferromagnetic interactions between the Tb^III ions in 2 . The profiles of χ_mT vs. T curves of 3 – 5 reveal that the magnetic properties of 3 – 5 are probably dominated by the thermal depopulation of the Stark sublevels of Ln^III ions.     

一种制备Schiff碱的新型方法

介绍了一种制备Schiff碱的新型方法——超音速气流固相法,其原理是在超音速气流下使芳醛和芳胺在反应器中摩擦活化,再通过撞击固定靶产生迅速的能量交换而发生化学反应.利用该方法成功制备了两种对氨基苯甲酸类Schiff碱,采用DTA对其反应进行了定性分析,并用IR、MS、1HNMR表征产物的结构,实验结果显示该方法制备Schiff碱无需溶剂,操作简单,反应时间短,转化率高.     

合成固载希夫碱配合物作为配体交换材料

Two new sporopollenin-immobilized Schiff bases, S-[N-(2-aminoetil) salicylaldiimino] and S-[N-(2-aminoetil) benzaldiimino], and their cobalt (Ⅲ) and nickel (Ⅱ) complexes, S-[N-(2-aminoetil) benzaldiimino] aquatriacetato cobalt (Ⅲ), S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (Ⅲ), S-[N-(2-aminoetil) benzaldiimino] diacetato nickel (Ⅱ), and S-[N-(2-aminoetil) salicylaldiimino] diacetato nickel (Ⅱ), were synthesized onto a chemically modified sporopollenin with ethylenediamine. The immobilized ligands and their metal complexes were characterized by thermal analysis and spectroscopic techniques such as infrared, ultraviolet-visible, and atomic absorption spectrometry. Immobilized Schiff base metal complexes, S-[N-(2-aminoetil) benzaldiimino] aquatriacetato cobalt (Ⅲ) and S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (Ⅲ), were used as ligand exchanger media to investigate ligand adsorption behavior of methylene blue (MB) with column technique. The result shows that the chelation of methylene blue with S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (Ⅲ) complex increases ligand adsorption capacity.     

含双水杨醛Schiff碱配体的双核配合物的合成及晶体结构

合成了4个含双水杨醛Schiff碱配体的双核过渡金属配合物,并通过元素分析、红外光谱、紫外光谱,热重分析以及X-射线单晶衍射等手段对所得配合物进行了表征。结果表明,配合物1、3和4都属于三斜晶系,空间群为P1,而配合物2属于单斜晶系,空间群为C2/c。在配合物1中,2个Cu髤离子具有不同的配位构型,其中一个Cu髤形成了五配位的四角锥构型,而另一个Cu髤形成了平面正方形构型。配合物4中,通过酚氧原子的桥联作用,双核单元相互连接形成了一维链状结构。     

由柔性配体庚二酸组装的微孔稀土配位高聚物

合成了3种新的庚二酸(H₂pim)稀土配位高聚物[Nd(Hpim)(pim)(H₂O)]_n·2nH₂O(1),[RE₂(pim)₃(H₂O)]_n·nH₂O[RE=Er(2),RE=Ho(3)],并通过元素分析红外光谱和单晶X射线衍射技术确定了其组成和晶体结构.配合物1为具有微孔的三维网状结构.配合物2和3同构,通过两种类型的O-H…O氢键将由配位键构筑的二维骨架结构组装成三维超分子结构.在这3个配合物中,庚二酸配体在同一配合物的结构中均存在不同的构象,体现了柔性配体不同于刚性配体的配位特点.     

基于半刚性乳酸衍生物的单一手性配位聚合物的合成、 结构与性质

在溶剂热反应条件下, 用预先合成的乳酸衍生物(R)-H₂CBA和(S)-H₂CBA分别与含氮辅助配体(E)-1,2-二(4-吡啶基)乙烯(DPEE)和1,4-二(1H-咪唑-1-基)苯(1,4-DIB)组合, 制备出2对不同结构的单一手性配位聚合物[Cd₂((R)-CBA)₂(DPEE)(H₂O)₂]_n(1-D), [Cd₂((S)- CBA)₂(DPEE)(H₂O)₂]_n(1-L), [Cd((R)-CBA)(1,4-DIB)]·H₂O(2-D)和[Cd((S)-CBA)(1,4-DIB)]·H₂O(2-L). 其中1-D和1-L是由梯形Cd-CBA链和DPEE配体连接成的二维框架结构; 而2-D和2-L是三维超分子框架结构, 包含3种不同类型的对映手性螺旋链. 对上述化合物进行了粉末X射线衍射、 热重分析和圆二色谱分析, 并对其荧光性质进行了讨论.     

Synthesis and Characterization of Lanthanide Metal Ion Complexes of New Polydentate Hydrazone Schiff Base Ligand

The new homodinuclear complexes of the general formula [Ln₂L₃(NO₃)₃] (where HL is newly synthesized 2-((2-(benzoxazol-2-yl)-2-methylhydrazono)methyl)phenol and Ln = Sm³⁺ (1), Eu³⁺ (2), Tb³⁺ (3a, 3b), Dy³⁺ (4), Ho³⁺ (5), Er³⁺ (6), Tm³⁺ (7), Yb³⁺ (8)), have been synthesized from the lanthanide(III) nitrates with the polydentate hydrazone Schiff base ligand. The flexibility of this unsymmetrical Schiff base ligand containing N₂O binding moiety, attractive for lanthanide metal ions, allowed for a self-assembly of these complexes. The compounds were characterized by spectroscopic data (ESI-MS, IR, UV/Vis, luminescence) and by the X-ray structure determination of the single crystals, all of which appeared to be different solvents. The analytical data suggested 2:3 metal:ligand stoichiometry in these complexes, and this was further confirmed by the structural results. The metal cations are nine-coordinated, by nitrogen and oxygen donor atoms. The complexes are two-centered, with three oxygen atoms in bridging positions. There are two types of structures, differing by the sources of terminal (non-bridging) coordination centers (group A: two ligands, one nitro anion/one ligand, two nitro anions, group B: three ligands, three anions).     

Syntheses and Crystal Structures of Two VO(IV) Schiff Base Complexes with Oxyammonia Ligand

1 INTRODUCTION The insulin-mimetic property of vanadium complexes is the most noteworthy finding and the relationship between vanadium and diabetes mellitus has been extensively studied in the past decades[1～5]. Vanadium complexes are capable of increa…     

Electrochemical Synthesis of MII Complexes with a Schiff Base containing an Amido Group. Crystal Structure of a Cobalt(II) Complex with a Reorganised Ligand

M(HL)(H₂O)_n complexes have been obtained by the electrochemical reaction of Fe, Co, Ni, Cu, Zn and Cd anodes with the potentially pentadentate and trianionic asymmetrical Schiff base 3‐aza‐N‐{2‐[1‐aza‐2‐(5‐nitro‐2‐hydroxylphenyl)‐vinyl]phenyl}‐4‐(5‐nitro‐2‐hydroxyphenyl)but‐3‐enamide (H₃L), containing a hard amido donor atom. The complexes have been characterized by elemental analysis, mass spectrometry, IR and ¹H NMR spectroscopies, magnetic measurements and molar conductivities. Co(HL)(H₂O) ( 2 ) has been found to rearrange in DMF solution into a crystallographically solved octahedral complex, CoL¹(H₂O)₂ ( 7 ) [where H₂L¹ is the symmetrical Schiff base ligand N,N′‐(1,2‐phenylene)‐bis(5‐nitro‐3‐hydroxysalicylidenimine)]. A hydrolysis mechanism is discussed to explain this rearrangement.     

1,10-邻啡啰啉取代的希夫碱配体及其双核配合物的合成

Recentstudyattentionsoncoordinationchem-istryhavebeendevotedtothedesignandsynthesisofmulti-dentateligandswithlarge仔-conjugationsystemsastheirabilitiesonintramolecularelectro/energy-transferevenifmostreportedligandscontainonlyonetypeofcoordinationsite(suc…     

Synthesis and Crystal Structure of a Co(II) Complex with Schiff Base and Imidazole Ligand

1 INTRODUCTION The chemical behavior of metal complexes with Schiff base ligand has attracted much attention be- cause of their catalytic activity in some industrial[1, 2] and biochemical processes[3~5]. As some metal com- plexes have shown the catalytic activity in some polymerization reactions[2, 6], we are recently inte- rested in polymerizartion of organo-silicon com- pounds catalyzed by Schiff base complexes of tran- sition metals. A series of Schiff base complexes have been prepare…     

Synthesis and Pyrolysis of Soluble Cyclic Hf-Schiff Base Polymers

Soluble Hf-containing polymers are significant processable precursors for the fabrication of ultra-high temperature ceramics. In this work, cyclic Hf-Schiff base polymers were synthesized via direct polymerization of hafnium alkoxide and bis-salen monomers. The defined structure and molecular weight of the polymers were characterized by NMR spectroscopy, gel permeation chromatography and MALDI-TOF mass spectroscopy. The feed ratio of monomers regulated the molecular weight and solubility of the polymers. This synthetic strategy features simple operation under ambient conditions, efficient reaction with high yield and cyclic polymers as the main products. The Hf-Schiff base polymers were converted to HfC/C materials after pyrolysis under argon at 1600 °C, which was identified by XRD measurements, elemental analyses and Raman spectroscopy. This work will inspire more precise and efficient synthesis and applications of metallopolymers.     

新型席夫碱大环化合物的合成

利用Mn^2＋, Ba^2＋作为模板离子, 由邻苯二胺和α,ω-二(3'-羟基-4'-甲酰苯氧基)取代烷[即1,4-二(3'-羟基-4'-甲酰苯氧基)丁烷、1,6-二(3'-羟基-4'-甲酰苯氧基)己烷、1,8-二(3'-羟基-4'-甲酰苯氧基)辛烷]反应分别合成了系列新型大环席夫碱化合物Lⁿ (n＝4, 6, 8). Mn^2＋用于L⁴合成, 并在洗涤时自动解络; L⁶和L⁸的合成以Ba^2＋模板, L⁶和L⁸的Ba^2＋配合物经与Na₂SO₄水溶液反应解络, 得到自由大环配体L⁶和L⁸. 上述新型大环席夫碱化合物采用元素分析, ¹H NMR, IR, 紫外-可见光谱和MS等进行组成和结构表征.     

Synthesis of Two Blue-light-emitting Complexes with Schiff Base Calixarene as the Ligand

Two new blue luminescent zinc and beryllium complexes with Schiff base calixarene derivative as the ligand were prepared.Their luminescent properties were determined,which indicated that they had strong blue fluorescent properties.They also had good solubility and film formation.These new complexes can be used as blue organic electroluminescent materials (OELMs) in organic electroluminescent devices.     

Study on Syntheses and Anti-bacterial Activities of Some New Transition Metal Complexes with Schiff Base Ligand Containing Pyridine and Amide Moieties

Several new transition metal complexes using Schiff base containing pyridine and amide moieties (N, N′-bis(β-salicylaliminoethyl)-2, 6-pyridinedicarboxylic amide, H4L) as the ligand have been prepared. Their compositions and structures are corroborated by elemental analysis, IR, UV, ^1H NMR, DTA-TG and molar conductivity data.Their anti-bacterial activities have been studied by microcalorimetry. The result shows that the ligand and all complexes are potential anti-bacteria reagent and their inhibitory capacities are concentration-depended. The Mn complex has the strongest inhibitory capacity.