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1.
Diorganotin derivatives of 2-mercapto-5-methyl-1,3,4 -thiadiazole, (R = Me 1, n-Bu 2, Ph 3, PhCH2 4), have been synthesized and characterized by IR, 1H, 13C and 119Sn NMR spectroscopy. Among them, polymer 2 was also characterized by X-ray crystallography diffraction analysis. This revealed that 2 showed a unique tricyclic structure consisting of a fused five-membered Sn2ON2 ring and a four-membered Sn2O2 ring. These formed a planar N2Sn3O2 skeleton, with distorted trigonal bipyramidal coordination at the two tin centers and a distorted octahedral coordination at the other tin center. The supramolecular structure of polymer 2 was a 1D zig-zag polymeric chain stabilized by intermolecular O–H...S hydrogen bonds. An erratum to this article can be found at  相似文献   

2.
Acrylonitrile‐styrene‐glycidyl methacrylate (N/S/G) terpolymers were prepared by bulk polymerization by using benzoyl peroxide as initiator and analyzed by NMR spectroscopy. The compositions of terpolymers were determined by quantitative 13C{1H}‐NMR spectra and compared with those calculated by Goldfinger's equation by using comonomer reactivity ratios: rNS = 0.04, rSN = 0.40; rNG = 0.22, rGN = 1.37; rSG = 0.44, rGS = 0.53. The 13C{1H}‐ and 1H‐NMR spectra were overlapping and complex. The spectral assignments were done with the help of distortionless enhancement by polarization transfer and two‐dimensional 13C‐1H heteronuclear single quantum correlation experiments. 2D total correlated spectroscopy was used to ascertain the various coupling between the protons. The methyl, methine, methylene, and oxymethylene carbon resonances showed compositional sensitivity. 2D nuclear Overhauser enhancement spectroscopy (NOESY) experiment was used to ascertain the spatial proton–proton couplings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1779–1790, 2003  相似文献   

3.
1,3-Thiazolidine-2,4-dione 2 has been synthesized by the cyclisation reaction of thiourea and chloroacetic acid in the presence of ethanol. The reaction of compound 2 with substituted aromatic aldehyde afforded the corresponding derivatives of substituted 5-benzylidene-1,3-thiazolidinone-2,4-dione 3a–d, which upon reflux with ω-bromoalkoxyphthalimide gave 2-{[-5-(substituted benzylidine)-2,4-dioxo-1,3-thiazolidine-3-yl]alkoxy} -1H-isoindole-1,3(2H)-dione 4a–i. Further, compounds 4a–i were treated with phenyl hydrazine and 2,4 dinitro phenyl hydrazine in the DMF to yield the title compound 2-[5-oxo-2,3-substituted diphenyl-2H-pyrazolo[3,4-d][1,3]thiazol-6(5H)-yl)alkoxy]-1H-isoindole-1,3(2H)-dione 5a–r. Structures of newly synthesized compounds were established based on elemental analysis, IR, 1H NMR and mass spectral data. Synthesized compounds have been assayed for their antibacterial activities against B. subtilis, K. pneumoniae, P. aeruginosa and S. aureus and antifungal activities against A. fumigatus and C. albicans.  相似文献   

4.
Two new organic–inorganic hybrid compounds [\textCu\textI ( \texten ) 2 ( \textH 2 \textO )] 2 { ( \textSiW\textVI 1 1 \textW\textV 1\textO 40 ) 2 [ \textCu\textII ( \texten ) 2 ( \textH 2 \textO )] 2 [\textCu\textII ( \texten ) 2 ] 2 }·6 \textH 2 \textO [{\text{Cu}}^{\text{I}} \left( {\text{en}} \right)_{ 2} \left( {{\text{H}}_{ 2} {\text{O}}} \right)]_{ 2} \left\{ {\left( {{\text{SiW}}^{\text{VI}}_{ 1 1} {\text{W}}^{\text{V}}_{ 1}{\text{O}}_{ 40} } \right)_{ 2} \left[ {{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} \left( {{\text{H}}_{ 2} {\text{O}}} \right)\left] {_{ 2} } \right[{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} } \right]_{ 2} } \right\}{\cdot}6 {\text{H}}_{ 2} {\text{O}} (1) and (H2 L)2[SiW12O40]·H2O (2) [en = ethylenediamine, L = 1,4-bis(3-pyridinecarboxamido)benzene], have been hydrothermally synthesized and characterized by IR, elemental analyses, TG analysis, and single-crystal X-ray diffraction. Structural analyses indicate that compound 1 exhibits an interesting three-dimensional(3D) cross-like supramolecular network through arrangement of a 1D organic–inorganic hybrid chain { ( \textSiW\textVI 1 1 \textW\textV 1 \textO 40 ) 2 [ \textCu\textII ( \texten ) 2 ( \textH 2 \textO )] 2 [\textCu\textII ( \texten ) 2 ] 2 } 2- . \left\{ {\left( {{\text{SiW}}^{\text{VI}}_{ 1 1} {\text{W}}^{\text{V}}_{ 1} {\text{O}}_{ 40} } \right)_{ 2} \left[ {{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} \left( {{\text{H}}_{ 2} {\text{O}}} \right)\left] {_{ 2} } \right[{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{ 2} } \right]_{ 2} } \right\}^{ 2- } . The compound 2 consists of protonated L ligand and [SiW12O40]4− anion. The protonated L ligands have been extended into a 2D network via hydrogen-bonding interactions. The guest [SiW12O40]4− clusters have been incorporated into the square voids of the 2D host network as templates. The electrochemical behavior and electrocatalysis of compound 2 bulk-modified carbon paste electrode (2-CPE) have been studied.  相似文献   

5.
Novel polymeric metal-free and metallo(Cu(II), Co(II), Ni(II), Zn(II) and Pb(II))–phthalocyanine complexes were synthesized using microwave irradiation and the products were purified by several (crystallization and preparative thin layer) techniques. The newly prepared compounds were characterized by a combination of elemental analyses, IR, 1H/13C NMR, 1H–1H COSY, MS and UV–Vis spectroscopy. In order to better understand the spectroscopy data (especially for 1H/13C NMR and 1H–1H COSY techniques), computational calculations were used for characterization at DFT/6-31G(d) level. The electronic spectra exhibited an intense π → π* transition with characteristic Q and B bands of the phthalocyanine core.  相似文献   

6.
Synthesis of four N-(heterocyclic)-9-aminoacridine derivatives was investigated. The synthesized compounds, N-thiazolyl-9-aminoacridine (AC1), N-(1,3,4-thiadiazolyl)-9-aminoacridine (AC2), N-(5-methyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC3), and N-(5-phenyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC4) were characterized by FT-IR, 1H NMR, mass-spectral, and elemental analysis. Amine-imine tautomerism was suggested by density functional theory (DFT) calculations. The optimized structures were obtained using B3LYP/6–311++G(d,p) level of theory. The UV–Vis absorption spectra were measured in various organic solvents. The synthesized compounds AC1–AC4 exhibit absorption spectra characteristic of typical donor–acceptor compounds. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) analysis have been used to explain the internal charge transfer (ICT) phenomena within the molecules. Also, simulated UV spectra were calculated using TD-DFT (B3LYP/6–311++G(d,p) and the results were compared with the experimental values.  相似文献   

7.
ABSTRACT

New unsymmetrically substituted naphthalene and perylene imide imidazoles, N-(2-ethylhexyl)-naphthalene-3,4-(4,5-dicyano-1,2-benzimidazole)-9,10-dicarboxyimide and N-(1-heptyloctyl)-perilene-3,4-(4,5-dicyano-1,2-benzimid-azole)-9,10-dicarboxyimide, were synthesized via condensation reactions of diaminophthalonitrile and aromatic monoimide monoanhydride derivatives. Their structural analyses have been conducted by using general spectroscopic methods including FT-IR, 1H- and 13C-NMR, mass and elemental analysis. The molecular structure of naphthalene derivative was also determined by single crystal x-ray diffraction. Electronic absorption and emission properties were investigated on comparison. For studied compounds, both DFT and TDDFT calculations were carried out with the 6-311G(d,p) basis set, taking into account solvation effects by means of polarizable continuum model as implemented in the Gaussian 09 package.  相似文献   

8.
The reactions of K3[Cu(CN)4], R3SnCl (R = Me or ph) and 2,3-dimethyl quinoxaline (dmqox) in H2O/acetonitrile media at room temperature afford the 3D-supramolecular coordination polymers (SCP) 3 [ \textCu 2 ( \textCN ) 2 \textdmqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 2} {\text{dmqox}}} \right] , 1 and 3 [ \textCu 2 ( \textCN ) 4 ·( \textPh 3 \textSn ) 2 ·\textdmqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{dmqox}}} \right] , 2. The structure of the tin free 1 consists of parallel zigzag chains connected by dmqox to form 2D-sheets containing hexagonal 18-atom fused Cu6(CN)4(dmqox)2 rings. The interwoven sheets along the a axis are close packed by extensive H-bonds developing 3D-network structure. The structures of 1 and 2 are investigated by elemental analysis IR, NMR and mass spectra. The ESI+ and ESI mass spectra of 2 support its polymeric nature while the ESI+ mass spectrum confirms the expected M. W. suggested by elemental analysis. The 13C-NMR spectrum of 2 supports the fact that the network structure of 2 contains the rhombic [Cu23-CN)2] motif. The structure of 2 was compared with the structure of the reported prototype 3 [ \textCu 2 ( \textCN ) 4 ·( \textPh 3 \textSn ) 2 ·\textqox ] ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{qox}}} \right] as well as the other related structures.  相似文献   

9.
Copolymers of N‐vinyl‐2‐pyrrolidone (V) and glycidyl methacrylate (G) monomers of different compositions were prepared by free‐radical solution polymerization. The copolymer composition of these copolymers was determined with 1H‐NMR spectra. The reactivity ratios calculated from the Kelen–Tudos and nonlinear least‐square error‐in‐variable methods were rV = 0.03 ± 0.01 and rG = 5.05 ± 0.84 and rV = 0.02 and rG = 4.72, respectively. The triad sequence distribution in terms of V and G centered triads was determined from 13C{1H}‐NMR spectroscopy. The complete spectral assignment of 13C{1H}‐ and 1H‐NMR spectra was performed with the help of distortionless enhancement by polarization transfer and two‐dimensional 13C–1H heteronuclear single quantum coherence. The 1H–1H couplings were explained with total correlation spectroscopy and nuclear Overhauser enhancement spectroscopy spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 50–60, 2002; DOI 10.1002/app.10186  相似文献   

10.
Petroleum ether insoluble fractions of a pyridine extract of a Japanese lignite were pyrolysed with tetralin. The chain length of alkyl groups bonded to aromatic rings and the average chemical structure of aromatic compounds in the lignite were obtained from analyses of hydrogenolysis products. Gas Chromatographic analyses of fractions eluted by cyclohexane showed the presence of C15 to C34 straight-chain alkanes. The chemical structures of the other fractions were analysed quantitatively by a combination of 13C and 1H n.m.r. The unit structure of petroleum ether insoluble fractions in the lignite consists of one to three aromatic rings with straight-chain alkyl groups, some of which are about 25–30 carbon atoms long.  相似文献   

11.
The kinetics of the catalytic oxidation of H2 on PtRu/C gas diffusion electrode (GDE) was studied by interfacing the electrode with aqueous electrolytes at different pH values. The conducting electrolytes were aqueous solutions of varying concentrations of KOH and HClO4 so that the pH was ranging between 2 and 13. The open circuit catalytic reaction rates exhibit the lowest value at pH = 13, while the catalytic activity is progressively increasing with decreasing pH values. The enhancement of the open circuit catalytic reaction rate can be even an order of magnitude higher in the acidic solution with respect to the alkaline electrolyte. It is shown that the nature of the aqueous electrolyte plays the role of an active catalyst support for the PtRu/C electrode, which drastically affects its catalytic properties. This is substantiated through the electrochemical equilibrium charge transfer reactions at the catalyst-electrode/electrolyte interface:
According to the aforementioned interaction, termed electrochemical metal support interaction (EMSI), the electrochemical potential of the electrons at the catalyst Fermi level is equalised with the electrochemical potential of the solvated electron in the aqueous electrolyte. The electrochemical promotion experiments carried out at various pH values showed that the non Faradaic modification of the catalytic activity is more intense when the catalyst-electrode is interfaced with electrolytes with high pH values where the OH ionic conduction prevails. It was concluded that similar to the solid state electrochemical systems the non Faradaic electrochemical modification of the catalytic activity proceeds through the formation of a polar adsorbed promoting layer of , electrochemically supplied by the OH species, at the three phase boundaries of the gas exposed gas diffusion catalyst-electrode surface.  相似文献   

12.
Three novel aromatic phosphorylated diamines, i.e., bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl} pyromellitamic acid (AP), 4,4′‐oxo bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl}phthalamic acid (AB) and 4,4′‐hexafluoroisopropylidene‐bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl}phthalamic acid (AF) were synthesized and characterized. These amines were prepared by solution condensation reaction of bis(3‐aminophenyl)methyl phosphine oxide (BAP) with 1,2,4,5‐benzenetetracarboxylic acid anhydride (P)/3,3′,4,4′‐benzophenonetetracarboxylic acid dianhydride (B)/4,4′‐(hexafluoroisopropylidene)diphthalic acid anhydride (F), respectively. The structural characterization of amines was done by elemental analysis, DSC, TGA, 1H‐NMR, 13C‐NMR and FTIR. Amine equivalent weight was determined by the acetylation method. Curing of DGEBA in the presence of phosphorylated amines was studied by DSC and curing exotherm was in the temperature range of 195–267°C, whereas with conventional amine 4,4′‐diamino diphenyl sulphone (D) a broad exotherm in temperature range of 180–310°C was observed. Curing of DGEBA with a mixture of phosphorylated amines and D, resulted in a decrease in characteristic curing temperatures. The effect of phosphorus content on the char residue and thermal stability of epoxy resin cured isothermally in the presence of these amines was evaluated in nitrogen atmosphere. Char residue increased significantly with an increase in the phosphorus content of epoxy network. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2235–2242, 2002  相似文献   

13.
Two diamine monomers, 4‐[4‐(1‐methyl‐1‐phenylethyl)phenoxy]‐1,3‐diamino benzene and 4‐{4‐[(4‐methylphenyl)sulfonyl]phenoxy}‐1,3‐diamino benzene, were synthesized, and both diamines were polycondensed with three commercial dianhydrides to obtain aromatic polyimides containing pendant groups. The polyimides were characterized by solubility tests, viscosity measurements, IR, 1H‐NMR, and 13C‐NMR spectroscopy, X‐ray diffraction studies, and thermogravimetric analysis. The polyimides had inherent viscosities of 0.33–0.58 dL/g in m‐cresol at 30 ± 0.1°C. All the polyimides were amorphous and were soluble in solvents such as N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidone, N,N‐dimethylformamide, and m‐cresol. Thermogravimetric analysis of the polyimides indicated no weight loss below 410°C under a nitrogen atmosphere. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1377–1384, 2005  相似文献   

14.
A new catalytic reaction of hydrogen sulfide decomposition is discovered, the reaction occurs on metal catalysts in gas phase according to equation $$2{\text{H}}_{2} {\text{S}} \leftrightarrow 2{\text{H}}_{2} + {\text{S}}_{2}^{{({\text{gas}})}}$$ 2 H 2 S ? 2 H 2 + S 2 ( gas ) to produce hydrogen and gaseous diatomic sulfur, conversion of hydrogen sulfide at room temperature is close to 15 %. The thermodynamic driving force of the reaction is the formation of the chemical sulfur–sulfur bond between two hydrogen sulfide molecules adsorbed on two adjacent metal atoms in the key surface intermediate and elimination of hydrogen into gas phase. “Fingerprints” of diatomic sulfur adsorbed on the solid surfaces and dissolved in different solvents are studied. In closed vessels in adsorbed or dissolved states, this molecule is stable for a long period of time (weeks). A possible electronic structure of diatomic gaseous sulfur in the singlet state is considered. According to DFT/CASSCF calculations, energy of the singlet state of S2 molecule is over the triplet ground state energy for 10.4/14.4 kcal/mol. Some properties of gaseous diatomic sulfur are also investigated. Catalytic solid systems, both bulk and supported on porous carriers, are developed. When hydrogen sulfide is passing through the solid catalyst immersed in liquid solvent which is capable of dissolving sulfur generated, conversion of hydrogen sulfide at room temperature achieves 100 %, producing hydrogen in gas phase. This gives grounds to consider hydrogen sulfide as inexhaustible potential source of hydrogen—a very valuable chemical reagent and environmentally friendly energy product.  相似文献   

15.
Two series of novel rod–coil block copolymers, poly(ɛ-caprolactone)-b-poly{2,5-bis[(4-methoxyphenyl) oxycarbonyl] styrene} (PCL-b-PMPCS) and poly{2,5-bis[(4-methoxyphenyl) oxycarbonyl] styrene}-b-poly(ɛ-caprolactone)-b-poly{2,5-bis[(4-methoxyphenyl) oxycarbonyl] styrene} (PMPCS-b-PCL-b-PMPCS), were successfully synthesized via atom transfer radical polymerization in chlorobenzene solution using macro-initiator and CuBr/Sparteine complex as catalyst. The results show that the number average molecular weight Mn increased versus the monomer conversion and that the polydispersity Mw/Mn was quite narrow (<1.35), which were the character of controlled polymerization. The structure of the block copolymers was experimentally confirmed by 1H NMR. And the liquid crystalline behavior of them was studied using DSC and POM. The data obtained implied that the block copolymers with low molar percentage of PMPCS block could show Tm of PCL. While only the copolymers with long rigid segment PMPCS could form liquid crystalline phase, which was quite stable with a high clearing point.  相似文献   

16.
Summary Thermally stable and optically active poly(amide-imide)s (PAIs) have been synthesized and their properties such as optical activity, solubility, thermal stability were studied. Polymers were synthesized by solution polymerization of 4,4’–(hexafluoroisopropylidene)-N,N’-bis-(phthaloyl-L-methionine) diacid chloride and various aromatic diamines by three different methods. The compounds obtained were characterized by elemental C, H and N analysis, solubility, FTIR, 1H NMR and 19F NMR spectroscopy. Thermogravimetric curves were also recorded. All data agree with the proposed structures.  相似文献   

17.
Two series of a-C(N):H films, with diamond-like character and graphite-like character respectively, are prepared. Without N incorporation, the two kinds of films have very close IR bands in the range of 1000–1800 cm 1. However, the difference in IR activity of the two series films became dramatical as N was introduced into both kinds of carbon films, which is attributed to purely electronic effect, the electronegativity of N. The N incorporated in carbon films is able to induce bond dipole of CC bonds in sp2 graphite cluster, leading to a degree of dipoles for all the aromatic sp2 CC bonds, a permanent electric dipole effect arises and this could lead to the increase in IR activity of the sp2 clusters. As the N content exceeds 20 at.% in the carbon films, strong conjugation of C≡N bonds with aromatic graphite rings can induce conjugated π bond dipole too.  相似文献   

18.
We have described a novel four-component reaction (4MCR) between oxalyl chloride 1, anilines 2a–h, and two molecules of ammonium thiocyanate 3 in acetone under ultrasound irradiation to give 3-aryl-2,4-dithioxo-1,3,5-triazepane-6,7-diones. A synthetically useful ultrasound effect was observed and title products were obtained in high yields after 15–35?min sonication. Our procedure compared to the conventional heating method has the benefit of higher reaction yields and shorter reaction times. The IR spectra showed the presence of N–H, C═O and C═S groups in these compounds and 1H, 13C NMR and Mass spectral results verified their structures. Cellular investigations showed that these compounds are toxic toward cancer cells.  相似文献   

19.
Copolymers of N‐vinylcarbazole and methyl methacrylate of different compositions were prepared by solution polymerization with azobisisobutyronitrile as an initiator, and their compositions were determined from quantitative 13C{1H}‐NMR spectroscopy. The reactivity ratios for the comonomers were calculated with the Kelen–Tudos and nonlinear error‐in‐variable methods. The complete spectral assignment of the overlapping 1H and 13C{1H} spectra of the copolymers was made with the help of distortionless enhancement by polarization transfer, two‐dimensional heteronuclear single‐quantum correlation, and total correlation spectroscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3005–3012, 2003  相似文献   

20.
The reactions of K3[Cu(CN)4], R3SnCl and bipodal ligands, where R = (n-Bu)3SnCl and L = quinoxaline (qox) and R = Me3SnCl and L = quinazoline (qaz) afford the red needle crystals of 3 [ \textCu2 ( \textCN )2 m\text-(qox) ]2 {}_{\infty }^{3} \left[ {{\text{Cu}}_{2} \left( {\text{CN}} \right)_{2} \mu {\text{-(qox)}}} \right]_{2} , 1 and the orange needle crystals of [Cu2(CN)2μ(qaz)]n, 2. 1 was subjected to single crystals X-ray study while 2 was investigated by IR, 1H NMR and mass spectra as well as TGA. The crystal structure of 1 exhibits puckered CuCN chains connected by qox molecules forming 2D-sheets. The 2D-sheets contain hexagonal nets stacked in A···A···A fashion. The paralleled sheets are close packed via extensive H-bonds, π–π stacking, strong Cu-Cu interaction and short Cu–C contacts which develop 3D-network. Unique rhombic [Cu23-CN)2] motifs result as consequence of interwoven of the 2D-sheets. The structure of 2 exhibits different XRPD pattern than that of 1 although, the two structures have the same Cu:CN:L stoichiometric ratio. The emission spectra of 1 and 2 display bands around 390, 420 and 475 nm corresponding to MC transition, 1(n,π*) → So and MLCT, respectively. Thus, 1 and 2 can be considered as examples of room-temperature luminescent Cu-containing polymers which can be used in applications as molecular sensing systems. Also, the oxidative degradation of Metanil Yellow (MY) dye has been investigated by hydrogen peroxide catalyzed by 1 or 2. The catalytic activity of 1 is more pronounced than that of 2.  相似文献   

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