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1.
The synthesis of carbazola substituted N-acylated polyethylenimines, namely, poly[N-(9-carbazolyl)acetylethylenimine] 20 and poly[N-(2-(9-carbazolyl))propanoylethylenimine] 21 by a grafting reaction onto PEI and isomerization polymerization of the carbazole substituted 2-oxazolines is reported. A complete acylation of amino groups in PEI by the 9-carbazolylacetyl groups was achieved by the p-nitrophenyl active ester method but PEI was only partially N-acylated by the 2-(9-carbazolyl)propanoyl groups under similar reaction conditions. The carbazole substituted 2-oxazolines, namely, 2-(9-carbazolyl)methyl-2-oxazoline 18 and (R,S)-2-[1-(9-carbazolyl)]ethyl-2-oxazoline 19 , were prepared by a base induced cyclization of ß-chloroamides. The ring-opening isomerization polymerization of 18 and 19 in the molten state with a cationic initiator (dimethyl sulfate, methyl triflate, or ethylene glycol ditosylate) gave 20 and 21. Gel permeation chromatography of 20 and 21 obtained with different monomerto-initiator ratios gave evidence of a chain transfer reaction with the monomer. The polymers were characterized by elemental analyses, IR, and 1H-NMR spectroscopy.  相似文献   

2.
Novel poly-Schiff bases (PSB's) that contain trans-1,2-bis(9-carbazolyl)cyclobutane(DCZB) units were synthesized by the direct polycondensation of trans-1,2-bis(3-formyl-9-carbazolyl)cyclobutane with aromatic diamines in n-amyl alcohol at 160°C. Complexation of these PSB's and of poly(vinyl DCZB) (PVDCZB) with iodine produced cation-radical salts which resulted form the transfer of an electron from DCZB moieties to iodine. All the undoped polymers were insulators having electrical conductivity of the order of 10?10–10?12 S cm?1 depending on the structure of polymers. By doping with iodine, the electrical conductivity increased by several orders of magnitude and reached a value of 10?3 S cm?1 in the case of PVDCZB and 10?5–10?6 S cm?1 in the case of PSB's. The electrical conductivity of doped PSB's increased with decreasing diamine length. PVDCZB having the same iodine content per carbazole unit as poly(9-vinyl-carbazole) (PVK) has a greater electrical conductivity than PVK.  相似文献   

3.
The preparation and radical-initiated polymerization of a carbazole-substituted N-acylated dehydroalanine, namely, 2-(9-carbazolyl)acetylaminopropenoic acid ( 7 ) and its methyl ester ( 6 ) is reported. The monomers 6 and 7 were prepared by dehydrochlorination of N-acylated β-chloroalanine derivatives. The monomer model compounds for the two polymers, namely, 2-(9-carbazolyl)acetylamino-2-methylpropanoic acid ( 11 ) and its methyl ester ( 10 ), were also prepared. The polymers and their monomer model compounds were characterized by elemental analysis, IR and 1H-NMR spectra. The polymers 12 and 13 of different molecular weights could be obtained by changing the monomer-to-initiator ratios used in polymerization experiments.  相似文献   

4.
A number of new (9-methyl-3-carbazolyl)arylpropenones were synthesized. Oxidation of them with alkaline hydrogen peroxide gave (9-methyl-3-carbazolyl)arylketo epoxides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1359–1361, October, 1973.  相似文献   

5.
Aryl substituted nitrile oxides undergo 3 + 2 cycloaddition to N-vinyl carbazole to afford only one regioisomer, i.e., 3-aryl substituted 5-(9-carbazolyl)-Δ2-isoxazolines III in good yield.  相似文献   

6.
《Chemical physics letters》1985,117(2):171-175
Photophysical properties of poly[2-(9-carbazolyl)ethyl methacrylate] film have been studied. This polymer shows a clear monomer fluorescence spectrum from carbazole chromophores and has no detectable excimer emission, even in the solid state. Highly efficient sensitized photoconductivity by electron acceptor doping shows effective electronic excitation energy migration through carbazole chromophores.  相似文献   

7.
The synthesis of N,N-diethyl-9-carbazolylacetamide ( 6 ), (R,S)- and (R)-N,N-diethyl-2-(9-carbazolyl)propanamide ( 7 ), N,N′-dimethyl-N,N′-di-(9-carbazolylacetyl)-1,2-ethanediamine ( 11 ), and (R)-N,N′-dimethyl-N,N′-di[2-(9-carbazolyl)propanoyl]-1,2-ethanediamine ( 13 ) is reported. The racemic compound, (R,S)-2-(9-carbazolyl)propanoic acid ( 2 ), was resolved by partial crystallization of the diastereomeric salts formed between 2 and (+)-α-methylbenzylamine. The 1H-NMR spectra of 6 and 7 showed magnetic nonequivalence of the chemically equivalent protons of the methyl and methylene groups in 6 and 7 due to partial double bond character of the amide bond. The upfield resonances corresponding to the two sets of methyl and methylene protons were assigned by the aromatic solvent-induced shift (ASIS) method to the protons anti to the carbonyl oxygen in the conformation of amide bond in 6 and 7 . The 1H-NMR spectra of 11 and (R)- 13 were used to determine the population of anti-anti, anti-syn (syn-anti) and syn-syn conformers in the structures of these dimer model compounds; the relative conformer populations were 0.45:0.47:0.08 and 0.28±0.02:0.29±0.01:0.43±0.01 in 11 and (R)- 13 .  相似文献   

8.
Several reactions occur during the initiation of 2-(9-carbazolyl)ethyl glycidyl ether polymerization by K, K+ (15-crown-5)2. At first the oxirane ring is opened mainly in the β-position. An organometallic intermediate obtained cleaved then the linear ether bond in the substituent and the cyclic one in crown ether. Various potassium alkoxides are finally formed. They are the real initiators of the polymerization. 9-Vinylcarbazole being another reaction product is inactive in this process.  相似文献   

9.
We investigated the photosensitizers effect on the photorefractive (PR) properties in five poly[methyl-3-(9-carbazolyl)propylsiloxane] (PSX-Cz)-based PR composites which were doped with various photosensitizers having each different electron affinity, such as 2,4,5,7-tetranitro-9H-fluorine-9yilden malonitrile (TeNFM), 2,4,7-trinitro-9-fluorenone (TNF), 9-dicyanomethylene-2,4,7-trinitro-fluorenone (TNFM), tetracyanoethylene (TCNE), and 7,7,8,8-tetracyanoquinnodimethane (TCNQ). At 632.8 nm, photo-charge generation efficiencies, photoconductivities, space charge field, four wave mixing diffraction efficiencies, and PR grating buildup times were measured as a function of external electric field. The photo-charge generation, which is dependent on the light absorption, was achieved through the charge transfer (CT) complexes between the PSX-Cz and each of the photosensitizers. The photon energy of the CT transition decreased with increasing electron affinity of the photosensitizer. In composites doped with TeNFM, TNF, and TNFM, the space charge field (Esc) increased as the photo-charge generation efficiency increased; the grating buildup in these composites is rate-limited by the photo-charge generation speed. In sample doped with TCNE, and TCNQ, the hole mobility was reduced due to the larger amount of photosensitizer anion traps produced by photoreduction of the photosensitizer. Then, the grating buildup speed became hole mobility limited, and smaller buildup rates were observed. The magnitude of space charge field was sustained as the charge and trap density increased. In all composites, the refractive index modulation is increased with the magnitude of space charge field.  相似文献   

10.
Time-resolved fluorescence spectra of poly-NE-(9-carbazolyl)carbonyl-L-lysine (PKL) excited by a picosecond laser have been constructed from many w  相似文献   

11.
An absorbance probe method was used for the investigation of photolysis of cationic photoinitiators. The rates of the photolysis of diphenyliodonium hexafluorophosphate (DPIH), diphenyliodonium tetrafluoroborate (DPIB), di(tert-butylphenyl)iodonium tetrafluoroborate (DTIB), di(tert-butylphenyl)iodonium bromate (DTIBr), triphenylsulfonium hexafluorophosphate (TPS) and cyclopropyldiphenylsulfonium tetrafluoroborate (CPS) were studied in the presence of acid indicator quinaldine red (QR) in acetonitrile. Diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate showed the highest photolysis rate. Photopolymerization of 1,3-di(9-carbazolyl)-2-propanol glycidyl ether (DCPGE) initiated with the iodonium and sulfonium salts in bulk and in solution was studied. It was established that the highest initial rate of polymerization is characteristic of DCPGE photopolymerization initiated with DPIH and TPS in bulk. The oligomers of DCPGE of number average molecular weight ( [`(Mn)]\overline{M_n} ) ranging from 710 to 1220 were obtained in these reactions in bulk and those with [`(Mn)]\overline{M_n} ranging from 1300 to 1600 were obtained in solution.  相似文献   

12.
The functional polymer containing carbazole unit, [(poly(9-(4-vinylbenzyl)-9H-carbazole) (PVBK)], was successfully prepared via nitroxide-mediated living free-radical polymerization of 9-(4-vinylbenzyl)-9H-carbazole (VBK). The controlled features of the polymerization were confirmed by the linear increase in the molecular weight with the monomer conversion while keeping the relative narrow molecular weight distribution (Mw/Mn ? 1.51), and successful chain extension with styrene. The resulting polymer absorbed light in the 305-355 nm range and exhibited fluorescent emission at 350 nm. The fluorescent intensity of the polymer was lower than that of monomer and was affected by the properties of the different solvents, which decreased in the following order: DMF > THF > CHCl3 at the same concentration of carbazole units. The fluorescence intensity of the polymer was apparently influenced by chromophore concentration, and the maximum value was obtained when the carbazole unit concentration was around 8 × 10−5 mol/L. Moreover, it was shown that the strong fluorescence of PVBK can be quenched by methyl acrylate (MA).  相似文献   

13.
An absorbance probe method was used for the investigation of photolysis of cationic photoinitiators. The rates of the photolysis of diphenyliodonium hexafluorophosphate (DPIH), diphenyliodonium tetrafluoroborate (DPIB), di(tert-butylphenyl)iodonium tetrafluoroborate (DTIB), di(tert-butylphenyl)iodonium bromate (DTIBr), triphenylsulfonium hexafluorophosphate (TPS) and cyclopropyldiphenylsulfonium tetrafluoroborate (CPS) were studied in the presence of acid indicator quinaldine red (QR) in acetonitrile. Diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate showed the highest photolysis rate. Photopolymerization of 1,3-di(9-carbazolyl)-2-propanol glycidyl ether (DCPGE) initiated with the iodonium and sulfonium salts in bulk and in solution was studied. It was established that the highest initial rate of polymerization is characteristic of DCPGE photopolymerization initiated with DPIH and TPS in bulk. The oligomers of DCPGE of number average molecular weight ( ) ranging from 710 to 1220 were obtained in these reactions in bulk and those with ranging from 1300 to 1600 were obtained in solution. Correspondence: Ruta Lazauskaite, Juozas V. Grazulevicius, Department of Organic Technology, Kaunas University of Technology, Radvilenu plentas 19, LT-50254 Kaunas, Lithuania.  相似文献   

14.
Dichloroacetylene (C2Cl2) reacts with carbazole and primary amines under phase-transfer catalytic (PTC) conditions to give 1-N-alkylimino-1,2-di(9-carbazolyl)ethanes (I) and 9-((E)-1,2-dichlorovinyl)carbazole (II) in one-step synthesis. Compounds I are formed from the addition of amines to the triple bond of C2Cl2 followed by reactions with carbazole.  相似文献   

15.
3-Acetyl-4-hydroxyphenyl acrylate (AHPA) was synthesized by treating acryloyl chloride with 2,5-dihydroxy acetophenone in the presence of triethylamine at 0 °C. AHPA was polymerized in ethyl methyl ketone (EMK) at 70 °C by free radical polymerization under nitrogen atmosphere using benzoyl peroxide as initiator. The monomer and the polymer were characterized by FT-IR, 1H-NMR and 13C-NMR spectroscopy. The polymer-metal complexes were obtained by the reaction of chloroform solution of poly(AHPA) with aqueous solution of Cu(II)/Ni(II) acetates. The polymer-metal complexes were characterized by FT-IR and the results revealed that the ligands are coordinated through the oxygen of the keto group and oxygen of the phenolic -OH group to the metal ions. The electronic spectra and magnetic moment of polymer-metal complexes showed an distorted octahedral and square planar structure for poly(AHPA)-Ni(II) and poly(AHPA)-Cu(II) complexes respectively. The X-ray diffraction studies revealed that while the polymer was amorphous the polymer-metal complexes were crystalline. The thermal stability and glass transition temperature of the polymer-metal complexes were found to be higher than that of the polymer.  相似文献   

16.
In this work, 9-(2-(benzyloxy)ethyl)-9H-carbazole (BzOCz) and 1-tosyl-1H-pyrrole (TsP) monomers were chemically synthesized and characterized by Fourier transform infrared reflectance (FTIR) and proton nuclear magnetic resonance (1H-NMR) spectroscopy. BzOCz and TsP were electrocoated on glassy carbon electrode (GCE) in various molar fractions (X TsP?=?0.5, 0.83, 0.91, and 0.98) in 0.1?M sodium perchlorate/acetonitrile. The detailed characterization of poly(BzOCz-co-TsP) was studied by cyclic voltammetry, FTIR-attenuated total reflection spectroscopy and electrochemical impedance spectroscopy (EIS). The effects of different molar fractions during the preparation of modified electrodes were studied by EIS technique. The AC impedance technique was used to determine the capacitive behaviors of modified GCE via Nyquist, Bode magnitude, and Bode phase plots. The highest low frequency capacitance value was obtained as C LF?=?23.94?μF?cm?2 for X TsP?=?0.98. Therefore, synthesized copolymer has more capacitive behavior than its homopolymers, such as C LF?=?7.5?μF?cm?2 for poly(BzOCz) and C LF?=?9.44?μF?cm?2 for poly(TsP). In order to interpret the AC impedance spectra, R(Q(RW)) electrical equivalent circuit was employed with linear Kramers–Kronig test. A mechanism for electropolymerization has been proposed for copolymer formation.  相似文献   

17.
In this study, the electropolymerization of 3-methylthiophene (3-MT) was preformed in the presence of a catalytic amount 1- (2-pyrrolyl)-2-(2-thienyl) ethylene (PTE) by cyclic voltammetry in acetonitrile as a solvent and lithium perchlorate as the electrolyte on a glassy carbon (GC) electrode. First, PTE was synthesized via the Wittig reaction. The addition of a catalytic amount of PTE during the electropolymerization of 3-MT changes the cyclic voltammograms such that the analysis of cyclic voltammograms of poly(3-MT) shows a considerable increase in the electroactivity and redoxability. Furthermore, the presence of PTE during the electropolymerization of 3-MT increases the polymerization rate. The CV measurement of the electron transfer ferro/ferricyanide redox system using different modified GC electrodes shows that the rate of charge transfer for poly(3-MT) in the presence of PTE is greater than that of poly(3-MT) alone. The conductivity of the obtained polymers was determined by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl (w/v) solutions. With the application of Zview(II) software to the EIS, we estimate the parameters of the proposed equivalent circuit, based on a physical model for the electrochemical behavior of coatings on the GC electrode, to be 15739 ohm cm2 for the charge transfer resistance (Rct) for poly(3-MT) alone and 9700 ohm cm2 for poly(3-MT) in the presence of PTE. Thus, the film of poly(3-MT) formed in the presence of PTE is more conductive.  相似文献   

18.
High quality free-standing poly (3-(4-fluorophenyl)thiophene) (PFPT) films with conductivity of 10−1 S/cm were electrosynthesized in boron trifluoride diethyl etherate (BFEE) by direct anodic oxidation of the monomer 3-(4-fluorophenyl)thiophene (FPT) on stainless steel sheet. As-formed flexible and shiny PFPT films can be cut into various shapes by a knife or a pair of scissors. The structure, thermal stability and morphology of PFPT films were studied by FT-infrared, UV-vis, Raman spectroscopy thermogravimetric analysis and scanning electron microscopy, respectively.  相似文献   

19.
The reaction of H2Os3(CO)10 with CF3CN in hexane at 80°C leads to two isomeric products. The isomer constituting the major product contains a 1,1,1-tri-fluoroethylidenimido ligand which bridges one edge of the Os3 triangle via the nitrogen, atom and may be formulated as (μ-H)Os3(CO)10(μ-NC(H)CF3) (I). The minor product, formulated as (μ-H)Os3(CO)10(μ-η2-HNCCF3) (II), contains a 1,1,1-trifluoroacetimidoyl ligand which is also edge-bridging, being N-bonded to one Os atom and C-bonded to the other. Thermolysis of I and II in solution results in loss of a CO group in each case to give (μ-H)Os3(CO)9?32-NC(H)CF3) (III) and (μ-H)Os3(CO)932-HNCCF3) (IV), respectively, which, it is proposed, are structurally related to I and II, but with the CN group coordinated also to the third Os atom in place of a CO group. In the case of IV this proposal has been confirmed by an X-ray crystallographic analysis. The compound crystallises in space group C2/c with a = 14.258(7), b = 13.486(10), c = 18.193(8) Å, β = 92.68(4)°, and Z = 8. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by full-matrix least squares to R = 0.054 for 2489 unique observed diffractometer data. Reaction of I with Et3P gives a 1 : 2 adduct which is formulated as (μ-H)Os3(CO)10[μ-N?C(H)(CF3)PEt3] (V) on the basis of NMR evidence.  相似文献   

20.
The results of the spectral and magnetochemical studies of some salts of the “sandwich-like” paramagnetic anion {NiIII5-π-(3)-1,2-B9C2H11]2} (I) with the Cs+, (CH3)4N+, and (C6H5)4P+ cations and the cation complex of Fe(II) and 1,10-phenanthroline, [FeIIPhen3]2+, are reported. The solid-phase IR, Raman, and X-ray photoelectron spectroscopy methods and optical spectroscopy of solutions were used. The effective magnetic moments (μeff) of Ni(III) in anion (I) were measured by the Faraday technique and corrected for the diamagnetism of the aromatic cluster ligands 1,2-B9C2H 11 2− (II). It is established that μeff is weakly dependent on the nature of the cation. The problems concerned with the nature of the metal-ligand bonds in metal-carborane systems like (I) are discussed. The hypothesis of the charge transfer from ligands (II) to the transition metal atoms is validated, the donor ability rows of the π-ligands are introduced, and the cluster structure of the systems under study is attested. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 6, pp. 1060–1071, November–December, 1996. Translated by I. Izvekova  相似文献   

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