Synthesis and properties of iron(II) tetra(1,4-dithiin)porphyrazine bearing peripheral long-chain alkyl group of active end-bromine

The novel tetra-(1,4-dithiin) metal-free (H₂Pz) and metalloporphyrazines (MPz, M = Mg, Fe) bearing peripheral tetrapropyl-bromine derived from 2,3-dicyano-5-propyl-bromine-1,4-dithiin, were synthesized in a multi-step reaction sequence. These complexes were characterized by ¹H NMR, IR, UV–vis, GC–MS, XPS and elemental analysis and their UV–vis spectra were discussed in detail. The iron(II) tetra-(1,4dithiin)porphyrazine bearing peripheral tetrapropyl-bromine was supported on an Amberlite CG-400 resin to form a biomimetic catalyst, the ability of which for activating O₂ and H₂O₂ was estimated from the degradation of Rhodamine B (RhB) under visible light irradiation (λ ? 420 nm). More than 70% of the RhB was degraded by O₂ in air for 24 h in the solution of pH 9.18 and by H₂O₂ only for 12 h in the solution of pH 3.0.     

四溴丙基四(1,4-二噻(口英))四氮杂卟啉锌的合成及其性能研究

以镁离子为模板,2,3-二氰基-5-溴丙基-1,4-二噻(口英)为前驱体,成功地合成了四溴丙基四(1,4-二噻(口英))四氮杂卟啉锌,用紫外光谱、红外光谱、元素分析和X-射线光电子能谱对其进行了表征,并将目标化合物负载到树脂上,初步考察了其对苯酚的光催化降解效果.     

四酰胺基四(1,4-二噻英)四氮杂卟啉的合成

以2,3-二氰基-5-酰胺基-1,4-二噻英为前驱体,利用镁模板法在较温和的条件下合成了四酰胺基四(1,4-二噻英)四氮杂卟啉自由配体,目标产物的终产率为42%,并通过1H-NMR、UV-Vis、XPS等表征手段进行了初步表征。有待进一步合成四酰胺基四(1,4-二噻英)四氮杂卟啉金属配合物。四酰胺基四(1,4-二噻英)四氮杂卟啉金属配合物可用于在模拟太阳光的条件下降解罗丹明B、甲基橙等染料。     

三(戊烷氧基)苯-一(1,4-二噻英)四氮杂卟啉的合成

前驱体2,3-二氰基-1,4-二噻英由顺式-1,2-二氰基-1,2-乙二硫钠盐与1,2-二溴乙烷反应生成,前驱体4-戊烷氧基邻苯二腈由正戊醇与4-硝基邻苯二腈反应得到,然后用"镁模板法"合成不对称的三(戊烷氧基)苯-一(1,4-二噻英)四氮杂卟啉,产率为43%。并对其自由配体进行了紫外光谱和Maldi-TOF MS表征。     

一种新型仿生化合物四甲基四(1,4-二噻)四氮杂卟啉锰的合成与表征

成功合成了新型化合物2,3-二氰基-5-甲基-1,4-二噻,进一步以其为前驱体用模板反应法合成出四甲基四(1,4-二噻)四氮杂卟啉锰,用紫外-可见光谱、红外光谱、元素分析和X-射线光电子能谱对配合物进行了结构表征。     

一种新型仿生化合物四甲基四(1,4-二噻(口英)四氮杂卟啉锰的合成与表征

成功合成了新型化合物2,3-二氰基-5-甲基-1,4-二噻(口英),进一步以其为前驱体用模板反应法合成出四甲基四(1,4-二噻(口英))四氮杂卟啉锰,用紫外-可见光谱、红外光谱、元素分析和X-射线光电子能谱对配合物进行了结构表征.     

四苯乙炔基硅烷的合成及热性能研究

为得到耐热的含有苯乙炔官能团的有机硅单体,通过苯乙炔锂(由苯乙炔与丁基锂制得)与四氯硅烷的反应,合成了四苯乙炔基硅烷(TPES),通过多次重结晶获得了纯度为99.5%的TPES,并用FTIR、1HNMR、13C NMR、29Si NMR及元素分析对其结构进行了表征。对TPES及其400℃固化物的DSC、FTIR和TGA的分析表明:TPES的熔融温度范围宽达113℃(199℃~312℃);在氮气中失重5%时的温度Td5为710.8℃,800℃残炭率高达93.3%,空气中的Td5为595℃,800℃残炭率也达58.3%,耐热性能十分优异,具备作为一种耐高温聚合物材料的优秀潜质。     

Synthesis and Characterization of Poly(tetramethyl-1,4-silphenylenesiloxane) Derivatives with Oxyethylene Substituent on Phenylene Moiety

Summary Novel poly(tetramethyl-1,4-silphenylenesiloxane) derivatives having 2-methoxy-ethoxy or 2-(2-methoxyethoxy)ethoxy substituents at both 2- and 5-positions on phenylene moieties were synthesized and characterized by differential scanning calorimetry and thermogravimetry analyses. Poly(tetramethyl-1,4-silphenylene-siloxane) derivatives were obtained by condensation polymerization of the corresponding disilanol derivatives, i.e., 1,4-bis(dimethylhydroxysilyl)-2,5-bis(2-methoxyethoxy)benzene and 1,4-bis(dimethylhydroxysilyl)-2,5-bis[2-(2-methoxy-ethoxy)ethoxy]benzene, which were prepared by the Grignard reaction using chlorodimethylsilane and the corresponding dibromobenzene derivatives followed by the hydrolyses, catalyzed by palladium on charcoal. The introduction of 2-methoxyethoxy groups on the phenylene moiety made the melting point high, compared with poly(tetramethyl-1,4-silphenylenesiloxane); however, that of 2-(2-methoxyethoxy)ethoxy groups made it low, indicating the longer oxyethylene moiety induced the lowering of the melting point. There were no significant differences in the thermostabilities of both present polymers, suggesting the length of oxyethylene moiety would not affect the thermostability, though the introduction of polar oxyethylene group onto the phenylene moiety induced a decline of thermostability.     

新型仿生分子四酯基四(1,4-二噻英)四氮杂卟啉及其金属配合物的合成与表征

以2,3-二氰基-5-酯基-1,4-二噻英为前驱体、以Mg2+为模板成功地合成了新型仿生化合物四酯基四(1,4-二噻英)四氮杂卟啉镁[MgPz(H3COOC-dtn)4]及其自由配体[H2Pz(H3COOC-dtn)4],用紫外可见光谱、红外光谱、质谱、X-射线光电子能谱对其进行了结构表征。     

一种新型四羧基(1,4-二噻英)四氮杂卟啉镁季铵盐的合成与表征

成功合成了四羧基(1,4-二噻英)四氮杂卟啉镁[MgPz(dtn-COOH)4]及其十六烷基三甲基铵盐[MgPz(dtn-COO-.CTA+)4],并通过紫外可见光谱、红外光谱和荧光光谱对其进行了表征。结果表明,季铵盐的形成很好地改善了四羧基(1,4-二噻英)四氮杂卟啉镁的溶解性能;季铵盐不仅易溶于常见的有机溶剂,还可以很好地溶于不同pH值的水溶液。     

Synthesis and properties of poly (1,4-cyclohexanedicarboxylic anhydride)

Summary Polyanhydrides from cycloaliphatic 1,4-Cyclohexanedicarboxylic acid (1,4-CHDA) were synthesized by melt polycondensation and characterized by WAXD, FTIR and DSC. The results show that these polymer displayed strong crystallinity with highly melting point and can't be dissolved in common solvents. The polymers, which come from different original isomer conformation CHDA, show different melting point and DSC curve. The isomerization happened during the polymerization and reached an equilibrium point at last. By melt polycondensation, the high cis-isomer content polyanhydride is difficult to obtained. Received: 24 May 2000/Revised version: 4 September 2000/Accepted: 6 September 2000     

Synthesis and properties of poly(tetramethyl-1,6-silpyrenylenesiloxane) derivative with phenyl groups on pyrenylene moiety

Poly(tetramethyl-1,6-silpyrenylenesiloxane) derivative with phenyl groups on pyrenylene moieties (P1) was prepared via polycondensation of disilanol monomer, i.e. 1,6-bis(dimethylhydroxysilyl)-3,8-diphenylpyrene (M1). P1 exhibited the very high glass transition temperature (T _g) of 191 °C. The temperature at 5% weight loss (T _d5) of P1 was 482 °C, indicating the relatively good thermostability of P1. P1 exhibited the bathochromic effect in the absorption and fluorescence spectra, indicating the expansion of π-conjugation by introducing phenyl groups onto pyrene skeleton as well as the σ–π and σ*–π* conjugation between pyrene and silyl moieties. In addition, P1 exhibited relatively weak excimer emission because of the inhibition of the excimer formation of pyrene skeleton by introduction of bulky phenyl groups onto pyrene skeleton. The fluorescence quantum yields (Φ_Fs) of M1 and P1 in chloroform were determined to be 0.46 and 0.37, respectively. It was revealed that M1 and P1 exhibited the higher fluorescence intensity than 1,6-diphenylpyrene, owing to the effect of the introduction of silyl moieties onto pyrene skeleton.     

熔融法无溶剂一步催化合成四（1,4-二噻英）四氮杂卟啉锰

首次以2,3-二氰基-1,4-二噻英为原料,钼酸铵为催化剂,四水合氯化锰为模板,用熔融法无溶剂一步合成了标题化合物,其结构经过UV-Via、IR、元素分析、X-射线光电子能谱(XPS)表征.     

Synthesis and properties of poly(ethylene-1,4-cyclohexanedimethylene naphthalate)

Copolyesters were synthesized from bis(hydroxyethyl) naphthalate/bis(hydroxymethylcyclohexane)naphthalate (BHEN/BHCN) with various compositions. Copolyesters having intrinsic viscosities of 0.58–0.65 dL g were obtained by melt polycondensation in the presence of metallic catalysts. The optimum condition for polyethylene-1,4-cyclohexanedimethylene naphthalate (PECN) copolyester manufacturing is the transesterification under a nitrogen atmosphere for 4 h at a temperature of 245 ± 5°C followed by polymerization under 2 mmHg for 50 min at a temperature of 290–320°C. Most copolyesters have better thermal stability than has poly(ethylene naphthalate) (PEN) and the effect of the cyclohexane–dimethylene structure on the thermal and crystalline properties of the resulting copolyesters was investigated using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures of the copolyesters were in the range of 115.2–138.4°C, and 10% weight losses in nitrogen were all above 453°C. The solubility, crystallinity, and moisture absorption of the copolyesters were also investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2245–2252, 1998     

Synthesis and characterizations of nanosized iron(II) hydroxide and iron(II) hydroxide/poly(vinyl alcohol) nanocomposite

Nanosized Fe(OH)₂ was synthesized by a coprecipitation method. Peaks between 500 and 1250 cm^?1 in Fourier transform infrared (FTIR) spectroscopy confirmed the presence of metal hydroxide stretching. X‐ray diffraction showed the suppressed crystalline system of Fe(OH)₂/aniline (ANI) due to the presence of a higher weight percentage of the dispersing agent, ANI. Thermogravimetric analysis implied that 75.5 wt % of residue remained up to 800°C. High resolution transmission electron microscope (HRTEM) analysis of Fe(OH)₂/ANI revealed that its size ranged from 10 to 50 nm with a rodlike morphology. Scanning electron microscopy implied that pristine Fe(OH)₂ had a nanotriangular platelet morphology, and a higher weight percentage of dispersing agent intercalated with Fe(OH)₂ had a spheroid with an agglomerated structure. The (UV–visible) spectrum implied the presence of Fe²⁺ ions at 326 nm and the existence of an amino group intercalated with Fe(OH)₂ showed a sharp peak at 195 nm, the intensity of which increased with increasing intercalated dispersing agent weight percentage. Photoluminescence showed that ANI‐intercalated Fe(OH)₂ showed a lesser intensity than the pristine Fe(OH)₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of soluble (porphyrinato)iron(II) polymers

The use of (tetrakis(4-hexylphenyl)porphyrinato)Fe(II) in polymerization reactions with bidentate ligands such as 9,10-diisocyanoanthracene and 1,4-diisocyanobenzene led to well-defined stacked polymers1 and2 which are still soluble in common organic solvents such as chloroform, dichloromethane, and tetrahydrofurane. They have been completely characterized by¹H-NMR and UV/vis spectropscopy in solution, even allowing end-group analysis for determination of the average degree of polymerization, yieldingn=10 andn=5 for1 and2, respectively. Mößbauer and IR spectroscopy further established the strong Fe-CN bonding reflected by very small isomer shifts and quadrupole splittings (E _Q0.2 mm s^–1) and a large decrease in the IR stretching frequency (v _CN60 cm^–1). The axially stacked polymers exhibit semiconducting properties only upon doping.Presented at the 5th International Symposium on Macromolecule-Metal Complexes (MMV), Summer 1993 in Bremen, Germany.     

Synthesis,structure and electrochemical properties of the cationic complex tris-(imidazolidine-1,10-phenanthroline)iron(II)

The complex [Fe^II(Imz-phen)₃](PF₆)₂, (Imz-phen = imidazolidine-[4,5-f]-1,10-phenanthroline) has been prepared and characterized using X-ray diffraction, UV–vis and IR spectroscopy, elemental analysis, fast atomic bombardment (FAB) mass spectrometry, and cyclic voltammetry. Its crystal lattice includes acetonitrile (π–π bound to phenanthroline), methanol, and water molecules. Scanning continuously between 1000 mV and 1650 mV in CH₃CN, a modified electrode that includes the iron (II) complex is obtained; after the 25th continuous cycle a stable film is formed that is electrocatalytically active in the reduction of sulfur oxoanions. When the electrocatalytic properties are evaluated in ethanol/water solution, the current achieved from the electroreduction of these sulfur species is linearly dependent on the respective concentrations, suggesting potential application in sulfite determination.     

Synthesis and study of photocatalytic oxide nanocomposites of titanium(IV) and cobalt(II)

The phase formation, texture, and photocatalytic activity of synthesized oxide nanocomposites of titanium(IV) and cobalt(II) have been studied in relation to the cobalt content and temperature of heat treatment. The high photocatalytic activity of optimum compositions has been recorded within the spectral range of visible light with λ ≥ 670 nm.     

Syntheses,structures and photocatalytic properties of three copper(II) coordination polymers

Three coordination polymers [Cu₂(obtz)₂(tdc)₂]_n (1), {[Cu(obtz)₂(H₂O)₂][Cu₂(obtz)₂(sip)₂]5.5H₂O}_n (2) and [Cu(obtz)(nip)]_n(3) were synthesized by the hydrothermal reaction (obtz = 1.2-bis(1,2,4-triazol-1-ylmethyl)benzene, tdc = 2.5-thiophenedicarboxylate, sip = 5-sulfoisophthalate, nip = 5-nitroisophthalate). 1 shows a ladder-like one-dimensional chain with two side arms. 2 is comprised of two distinct and crystallographically independent polymeric motifs. The first motif in 2 is the ladder-like one-dimensional anionic chain with two side arms. The second motif in 2 is the cationic chain. 3 exhibits the intriguing 2-fold interpenetrated network based on the undulated 2D (4.4) network. 1, 2 and 3 are good photocatalysts for the degradation of methyl orange (MO) under UV irradiation.     

Synthesis of 1,4-dihydropyridine derivatives using nanocrystalline copper(II) oxide catalyst

Nanocrystalline copper(II) oxide catalyzed three-component coupling of aromatic amines, β-ketoesters and cinnamaldehyde to afford the corresponding 1,4-dihydropyridines in moderate to good yields under mild conditions is described. The catalyst can be recovered and reused for four cycles with almost consistent activity.