基于多羧酸烟酸配体的镝、钬、铒和铥配合物的合成及荧光、磁学性质的表征

以5-(4-羧基苯氧基)烟酸配体(H₂cpna)和稀土金属离子Dy³⁺、Ho³⁺、Er³⁺和Tm³⁺为原料,采用水热法合成了4种稀土金属配合物[M(Hcpna)(cpna)(H₂O)₃]_n,其中M=Dy(1)、Ho (2)、Er (3)、Tm (4)。单晶X射线衍射分析表明配合物1、2、3和4为同构配合物,均为一维链状结构。通过红外、元素分析以及粉末X射线衍射对所得配合物进行了表征,同时对配合物的荧光和磁学性质开展了研究。荧光测试结果表明,配合物1～4的荧光强度均低于配体H2cpna的荧光强度。在2～300 K温度范围内1 kOe直流电场下测试了配合物1～4的磁性,结果表明配合物1、2、3和4的χ_mT值分别为14.04、14.15、11.08和6.83 cm³·mol^-1·K,与文献理论值相符合。     

Experimental and Computational Studies of Charge-Transfer and Reduction Products of 1, 4, 5, 8, 9, 11-Hexaazatriphenylene-Hexacarbonitrile: HAT-(CN)<Subscript>6</Subscript>

The compounds HAT-(CN)₆ · C₇H₈ · CH₃CN, 1, {[(Cp)₂Co][PF₆]}₃HAT-(CN)₆, 2, {([n-Bu₄N][I])₃HAT-(CN)₆]₂} · 3C₆H₆, 3, were prepared and characterized by X-ray crystallography (HAT-CN₆ = hexaazatriphenylene-hexacarbonitrile). The bonding in the neutral form of HAT-CN₆, (1), is compared to the co-crystallized examples of (HAT-CN₆) with [Cp₂Co][PF₆] (2) and [n-Bu₄N][I] (3). In the case of (3), the structure consists of layers of HAT-CN₆ molecules and four positions of three partially occupied I^- anions, one of which participates in a columnar stacking arrangement with HAT-CN₆. The nearly black color of crystals of (3) as compared to the light green color of (1) and the dark green color of (2) indicates that significant charge-transfer is occurring between the I^- ion and the HAT-CN₆ molecules. In addition to investigating the structures of various HAT-CN₆ containing samples, the one- and two-electron reduction products K[HAT-(CN)₆] and K₆[HAT-CN₆] were prepared by treatment of HAT-CN₆ with appropriate equivalents of K metal and EPR studies were undertaken. The results support the conclusion that the mono-radical is a typical S = 1/2 species and that the doubly-reduced species is a di-radical with a triplet ground state. Density functional theory calculations were carried out on the neutral, mono-anionic, and di-anionic forms of HAT-CN₆ to deduce the ground state geometry and spin state of each molecule. The theoretical results are in accord with the lowest energy ground state of [HAT-CN₆]^2- being a triplet state.     

金和银氮杂环卡宾原子簇化合物的合成结构与细胞毒性研究

由[Ag₃L₂(CH₃CN)₂](PF₆)₃(1,L=bis(N-pyridylimidazoliumyl)methane)通过金属转移反应合成了含有氮杂环卡宾配体的金银混合原子簇化合物,[Au₂AgL₂(CH₃CN)₂](PF₆)₃(2)和[Au₄AgL₄](PF₆)₅(3),用X-射线单晶衍射确定了2和3的晶体结构。化合物1和2结构相同,3个金属原子三角形排列。化合物3中5个金属原子呈链状排列,其中银原子居于中间。这些化合物在室温下分别在417,415和457 cm^-1处表现荧光。用MTT实验方法研究了对HuH7,C6和A375肿瘤细胞的毒性,其毒性顺序为1>2>3与这些化合物中银含量顺序相一致。     

Synthesis,crystal structure,spectroscopy, thermal properties and carbonic anhydrase activities of new metal(II) complexes with mefenamic acid and picoline derivatives

The mononuclear six metal(II) complexes ([Co(mef)₂(3-pic)₂(CH₃OH)₂] (1), [Ni(mef)₂(3-pic)₂(CH₃OH)₂] (2), [Cu(mef)₂(3-pic)₂] (3), [Co(mef)₂(4-pic)₂] (4), [Ni(mef)₂(4-pic)₂] (5), and [Cu(mef)₂(4-pic)₂] (6) with mefenamic acid and picoline ligands were synthesized, characterized, and their carbonic anhydrase inhibitory activities were evaluated. The six complexes were characterized by elemental analysis, FT-IR spectroscopy, and thermal analyses. The crystal structures of 1, 3, and 6 were determined by X-ray crystallography. The complexes have octahedral geometry. In 1, the mefenamato ligand behaved as monodentate whereas in 3 and 6, the mefenamato ligand acted as a bidentate ligand. Complexes 3 and 6 consist of the mefenamate and 4-picoline ligands. In 1, unlike the other complexes, methanol acted as a ligand and was involved in the coordination. Carbonic anhydrase I and II isoenzymes were purified from human erythrocytes. The in vitro effects of mefenamic acid, 3-picoline, 4-picoline, and the six metal(II) complexes on these isoenzymes were evaluated.     

Synthesis,crystal structure,spectral and electrochemical characterization,DNA binding and free radical scavenging studies of ferrocene-based thioureas

Abstract

Thioureas are important building blocks in medicinal chemistry; ferrocenes as highly hydrophobic moieties induce very interesting qualities in medicinal compounds. In this article, we have synthesized four ferrocene incorporated N,N′-disubstituted benzoyl thioureas (3a–3d) with general formula C₅H₅-Fe-C₅H₄C₆H₄Cl-NH-CS-NH-CO-C₆H₄(H/CH₃). Molecular structures of these compounds were characterized in solid and solution phases. In solution molecular structures were established by ¹H and ¹³C NMR and cyclic voltammetry. In the solid state their structures were characterized by elemental analyses and FTIR spectroscopy. Two of the compounds (3a and 3d) had also been structurally determined by single crystal X-ray diffraction analysis. The electrochemical characterization showed a reversible process with one electron transfer from Fe(II) to Fe(III). The single crystal analysis showed strong intermolecular non-covalent interactions in these compounds. Molecular structures of these compounds were also studied by density functional theory (DFT) calculation . DFT studies showed good correlation between calculated parameters and experimental results of solution phase and solid state characterizations. Compounds 3a–3d were evaluated for DNA interaction and antioxidant activity. These compounds interact with DNA via electrostatic forces and liberate significant binding constants and energies. Antioxidant potential –CSNH and –CONH groups induce same level of free radical scavenging ability in these compounds.     

Syntheses,crystal structures,and properties of nickel and cadmium complexes containing imidazole derivatives

[Ni₃(C₁₃H₉N₂O)₅(CH₃OH)₂] (1) and [Cd(C₁₂H₈N₃)₃] (2) were synthesized in methanol and characterized by elemental analyses, IR spectra, and X-ray diffraction. Complex 1 is trinuclear with three unsymmetric Ni(II)'s having different coordinated environments bridged by four oxygen atoms from five ligands. Intermolecular antiferromagnetic interactions were observed in 1. Complex 2 is mononuclear with Cd(II) six-coordinate by six nitrogen atoms from three bidentate HPBM anions. Complex 2 shows emission maxima in the blue region.     

Complexes of nickel(II) carboxylates with pyridine and cyclam: crystal structures,mesomorphisms, and thermoelectrical properties

Nickel(II) carboxylates [Ni(CH₃(CH₂)₁₄COO)₂(H₂O)₂] (1) and [Ni(C₆H₅COO)₂(H₂O)₂] (2) were obtained from reactions of NiCl₂·6H₂O with CH₃(CH₂)₁₄COONa and C₆H₅COONa, respectively. Complex 1 reacted with pyridine (pyr) to form [Ni(CH₃(CH₂)₁₄COO)₂(pyr)₂(H₂O)₂] (3) and [Ni₂(μ₂-H₂O)(CH₃(CH₂)₁₄COO)₄(pyr)₄] (4) in the same reaction mixture, and reacted with cyclam to form an ionic complex, [Ni(CH₃(CH₂)₁₄COO)(cyclam)(H₂O)]CH₃(CH₂)₁₄COO·4H₂O (5). In contrast, 2 reacted with cyclam to form [Ni(C₆H₅COO)₂(cyclam)] (6). Finally, 6 reacted with p-(hexadecyloxy)pyridine (L) to form an ionic complex, [Ni(cyclam)(L)₂](C₆H₅COO)₂ (7). Complexes 3–6 were single crystals. All complexes have octahedral Ni(II) center(s) and were magnetic. Complexes with cyclam as co-ligand were more thermally stable than those with pyridine and its derivative, L. Complexes 3 and 4 were mesomorphic after partial loss of water and/or pyridine ligands on heating. The ionic complexes 5 and 7 were not mesomorphic, but showed good thermoelectrical behavior with negative S_e values in CHCl₃ (?0.28 mV K^?1 for 5; -0.39 mV K^?1 for 7) and positive S_e values in C₂H₅OH (+0.25 mV K^?1 for 5; +0.20 mV K^?1 for 7).     

Synthesis and Solid-State Molecular Structure of Bi(silacyclohexyls) C5H10SiX-XSiC5H10 with X = H,PH, F,CL, BR,and I

The synthesis and purification of novel bi(silacyclohexyls) C₅H₁₀SiX-XSiC₅H₁₀ with X = H (1), Ph (2), F (3), Cl (4), Br (5), and I (6), which are composed of two silacyclohexyl rings connected by a silicon–silicon single bond, is described. Molecular structures for 2, 4, 5, and 6 were determined employing X-ray crystallography. Surprisingly, the SiSi bond lengths increase in the order I < Br < Cl, contrary to what is observed for methylated disilanes Me₂XSiSiXMe₂. The bond lengthening can be traced back to 1, 3 nonbonded interactions between the halogen atoms and the axial hydrogen atoms in the SiC₅ ring, which also cause a decrease of the SiSiX bond angles with increasing size of the halogen atom. Both rings substitute each other in the equatorial position for 4, 5, and 6, but in the axial position for 2.     

Synthesis,structure, EPR,and DFT calculation on dinuclear paddle wheel Cu(II) complexes with bis-chelate rings

A series of diester-dicarboxylic acids, L¹H₂, L²H₂, L³H₂, L⁴H₂, and L⁵H₂ and their dinuclear Cu₂ complexes [Cu(L¹)CH₃CN]₂ (1), [Cu(L²)H₂O]₂ (2), [Cu(L³)CH₃CN]₂ (3), [Cu(L⁴)EtOH]₂ (4), and [Cu(L⁵)CH₃CN]₂ (5), were synthesized. The crystal structures obtained for 1, 2, and 4 and the density functional theory optimized structures for 2, 3, and 5 illustrated the formation of tetracarboxylate “paddle wheel” complexes. The phthalyl and diphenyl head groups and the spacer moieties were appropriately altered and the size of the chelate ring expanded from 15-membered in 1 to 21-membered in 5. The dinuclear units have strong Cu–Cu interaction with EPR spectra exploring spin coupled features.     

Synthesis,structure, and fungicidal activity of thia- and aza-ferrocenophanes

Reaction of bridging dicyclopentadienyl disodium E(CH₂COCpNa)₂ (E = S or NPh, Cp = cyclopentadienyl) with FeCl₂ yields thia- and aza-[5]ferrocenophanes E(CH₂COCp)₂Fe [E = S (1) and NPh (2)]. Treatment of C₁₄H₈(CH₂SCH₂COCpNa)₂ (C₁₄H₈ = 9,10-anthracenyl) with FeCl₂ affords dithia-[12]ferrocenophane C₁₄H₈(CH₂SCH₂COCp)₂Fe (3), while similar reaction of C₆H₄(CH₂SCH₂COCpNa)₂ (C₆H₄ = 1,4-phenyl) with FeCl₂ provides a mixture of dithia-[12]ferrocenophane C₆H₄(CH₂SCH₂COCp)₂Fe (4) and tetrathia-[12,12]ferrocenophane [C₆H₄(CH₂SCH₂COCp)₂Fe]₂ (5), which are separated easily by column chromatography. These five compounds were characterized by IR and NMR spectroscopic analyses and the structures of 2 and 3 were further confirmed by single crystal X-ray diffraction. The electrochemical behaviors of 1–4 were investigated by cyclic voltammetry. In addition, their fungicidal activities against Alternaria solani, Cercospora arachidicola, Physalospora piricola, and Botrytis cinerea were tested in vitro.     

Synthesis and structures of silicon-, germanium-, and tin-containing imido-alkyl molybdenum complexes (ArN)2Mo(CH2EMe3)2 (E = Si, Ge, Sn)

New silicon-, germanium-, and tin-containing imido-alkyl molybdenum complexes (ArN)₂Mo(CH₂EMe₃)₂ (Ar is 2,6-diisopropylphenyl; E = Si (1), Ge (2), Sn (3)) were prepared in the crystalline state in 58–66% yields by the reactions of the (ArN)₂MoCl₂(DME) complex with alkyllithium derivatives Me₃ECH₂Li (E = Si or Ge) or the Grignard reagents Me₃ECH₂MgCl (E = Ge or Sn). The structures of complexes 1–3 and the known analog (ArN)₂Mo(CH₂Bu^t)₂ (4) were established by X-ray diffraction analysis. Complexes 1–3 were found to be isostructural. The coordination environment about the Mo atom can be described as a distorted tetrahedron. Complex 4 has a similar structure. The Mo-C distance tends to decrease with increasing electron donating ability of the EMe₃ group.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 597–600, March, 2005.     

两个镧系金属配合物的水热合成、晶体结构、荧光、热稳定性及抑菌活性

水热法合成了2个镧系配合物[Ln(3,4-DFBA)₃(phen)(H₂O)]₂(H₂O)₂(Ln=Sm (1),Ho (2);3,4-DFBA=3,4-二氟苯甲酸, phen=菲咯啉)。利用X-射线单晶衍射仪测定了配合物的晶体结构。配合物1和2结构相同,配位数为8,属于三斜晶系,空间群为P1。相邻的2个双核分子之间通过分子间氢键作用形成了2D层状结构。并用元素分析,红外,紫外,XRD等手段对目标配合物进行了表征。用TG-DTG技术测定了配合物的热稳定性,同时对配合物1的荧光性能进行了研究。另外,还测定了这两种配合物对白色念珠菌,革兰氏阳性菌(大肠杆菌)以及革兰氏阴性菌(金黄色葡萄球菌)的抑菌活性。     

Synthesis,characterization, and polyphenol oxidase activity of CuII,MnII, and FeIII complexes with a N2O2 ligand

To explore the effect of the metal center on catechol oxidase and tyrosinase activities, four complexes, Cu₂(μ-Cl)₂(hbpg)₂ (1), [Cu₂(μ-OH₂)₂(hbpg)₂](NO₃)₂(H₂O)₂ (2), [Fe₂(μ-Cl)₂(hbpg)₂]Cl₂(H₂O)₂ (3), and [Mn₂(μ-Cl)₂(hbpg)₂](H₂O)₂ (4) (hbpg?=?N-(2-hydroxybenzyl)-N-(2-picolyl)glycine), were synthesized and characterized with elemental analysis, single-crystal X-ray diffraction, molar conductivity measurements, mass spectrometry, UV-Visible, and FT-IR spectroscopies. The X-ray crystal structural analysis indicates that 1 has a binuclear copper, coordinated with N₂O₂ ligands. Complementary characterizations suggested that 2, 3, and 4 have similar coordination sphere. Complex 3 exhibits much higher catechol oxidase and tyrosinase-like activity than 1, 2, and 4. The results suggested that with a similar coordination sphere, the redox potential of the metal center is critical for catalytic activity. This work provides valuable information for improving the polyphenol oxidase activity of metal complexes for phenolic degradation.     

Synthesis of New Fused 1,5-Benzodiazepines,Part 3

1,3-Dihydro-4-phenyl-1,5-benzodiazepin-2-one 1 _a was treated with some ylidenecyanothioacetamides to give the corresponding pyrido(2,3-b)benzodiazepines 3– 6. Treatment of compound 1 _a with a mixture of thiophen-2-aldehyde and thiourea or guanidine gave the corresponding 1,3-thiazino- and pyrimido(4,5-b)benzodiazepines 7 and 8. 3-Arylidene derivatives 9 _a–e and 10 were synthesized. Compound 10 was subject to react with 2-(1-methylthio-1′-anilinomethylidene)malononitrile to give oxazino-benzodiazepine 11. Thieno(3,2-b)benzodiazepines 12 _a,b and 13 were synthesized via the reaction of compound 1 _b with sulfur and some active nitriles. [1,3-Dihydro-4-phenyl(1,5)-benzodiazepin-2-ylidene]malononitrile 15was used as synthon to obtain novel pyrido-, pyrano-, benzo-, and thienobenzodiazepines 16–20, respectively. The reaction of compound 1 _b with CS ₂ or PhNCS along with 1,1,3-tricyano-2-aminoprop-1-ene, 2-(1-methylthio-1′-anilinomethylidene)malononitrile, or 1,3-dibromopropane gave the corresponding polyfused benzodiazepines 21– 23, respectively.     

Synthesis,characterization, and crystal structure determination of palladacycles of para-substituted 2-thiobenzylazobenzenes

Bichelated neutral palladacycles (1–3), [Pd(L)Cl], were synthesized from reaction of the new potential tridentate (C,N,S) ligands, 2-thiobenzylazobenzene (L₁), 4′-methyl-2-thiobenzylazobenzene (L₂), and 4′-chloro-2-thiobenzylazobenzene (L₃) with sodium tetrachloropalladate(II), Na₂[PdCl₄], in ethanol. The compounds were characterized by elemental analysis, FT-IR, ¹H NMR, UV–visible, and thermogravimetric analysis. The crystal structures of L₂ and 1–3 were determined by single-crystal X-ray diffraction. In 1–3, the geometry around palladium remains almost square planar, coordinated to carbon, nitrogen, and sulfur of the ligand forming a bichelated cyclopalladate complex. The C–H…Cl type intermolecular hydrogen bonds, weak π…π, C–H…π, and van der Waals interactions are believed to be the stabilizing forces for the crystal packing of these palladacycles.     

Synthesis, electrochemical, and gas sensitivity performance of polyaniline/MoO3 hybrid materials

Hybrid material of polyaniline with molybdenum trioxide (MoO ₃ ) xerogel obtained by ion exchange of (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O was synthesized via polymerization of the monomer by ammonium peroxydisulfate/HCl oxidant system. The properties of MoO ₃ and hybrid material were investigated through thermogravimetry, X-ray diffraction, scanning electron microscopy, charge–discharge test, cyclic voltammetry, electrochemical impedance spectroscopy, and gas sensing experiments. Results show that hybrid material exhibits higher capacity, more excellent cycling reversibility, and better sensitivity to ethanol gas than MoO ₃ xerogel.     

Dinuclear copper(II) complexes of Fenoprofen: synthesis,spectroscopic, thermal,and SOD-mimic activity studies

Three dinuclear copper(II) complexes with the anti-inflammatory drug Fenoprofen [Hfen, 2-(3-phenoxyphenyl)propionic acid] and nitrogen donors of general formula [Cu₂(fen)₄(L)] _n were prepared from [Cu₂(fen)₄(dmf)₂]·2H₂O (1) [dmf?=?N,N′-dimethylformamide; L?=?4,4′-bipyridine (2), pyrazine (3), and 2,5-dimethylpyrazine (4)]. The new complexes were characterized by chemical analysis, spectroscopic, and thermogravimetric techniques. Antioxidant properties of 1–4 were evaluated for superoxide-dismutase-mimic activity employing the XTT method. Complex 2 presented the highest antioxidant activity (IC₅₀?=?0.260?µmol?L^?1). Anti-inflammatory properties of 2 were evaluated employing carrageenan-induced paw edema in mice, revealing that the Fenoprofen–copper(II) complex containing 4,4′-bipyridine does not present enhanced anti-inflammatory activity compared to the uncomplexed parent drug Fenoprofen calcium salt.     

Synthesis,structures, luminescent and dielectric properties of lanthanide coordination polymers

Under hydrothermal conditions, four lanthanide coordination polymers were synthesized based on 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H₃DCImPyO), with the molecular forumulas [Eu(HDCImPyO)·(H₂O)₂·(CHO₂)]_n (1), [Sm(HDCImPyO)·(H₂O)₂·(HCO₂)]_n (2), {[La(HDCImPyO)·(H₂O)·(HCO₂)]·O₂}_n (3) and {[Y(HDCImPyO)·(C₂O₄)·(H₂O)₂]·H₂O}_n (4). With diverse coordination modes, they were further characterized by elemental analysis, infrared spectroscopy, dielectric measurement, and single-crystal X-ray structural analysis. Complexes 1 and 2 were isostructural and had similar structures with {4⁴, 6²} topology. Complex 1 exhibited strong fluorescent emission in the solid state at room temperature. In 3, HDCImPyO^2? adopted μ₄-kO, O′: kO′, O′′: O′′′: O′′′′ coordination to bridge four La(III) ions to form a 3-D framework with {4. 5²}₂{4². 5¹⁰. 6¹². 7. 8³} topology. In 4, both HDCImPyO^2? ligands and Y³⁺ cations were simplified as linkers to form an interpenetrating 3-D framework with {4¹³. 6²}₂{4²². 6⁶} topology.     

Synthesis,spectroscopic properties,and antimicrobial activity of some new 5-phenylazo-6-aminouracil-vanadyl complexes

Six complexes, [VO(L¹-H)₂]?·?5H₂O (1), [VO(OH)(L^2,3?H)(H₂O)]?·?H₂O (2,3), [VO(OH)(L^4,5?H)(H₂O)]?·?H₂O (4,5), [VO(OH)(L⁶?H)(H₂O)]?·?H₂O (6), were prepared by reacting different derivatives of 5-phenylazo-6-aminouracil ligands with VOSO₄?·?5H₂O. The infrared and ¹H NMR spectra of the complexes have been assigned. Thermogravimetric analyses (TG, DTG) were also carried out. The data agree quite well with the proposed structures and show that the complexes were finally decomposed to the corresponding divanadium pentoxide. The ligands and their vanadyl complexes were screened for antimicrobial activities by the agar-well diffusion technique using DMSO as solvent. The minimum inhibitory concentration (MIC) values for 1–4 and 6 were calculated at 30°C for 24–48?h. The activity data show that the complexes are more potent antimicrobials than the parent ligands.