四(2,4-二特戊基苯氧基)酞菁铜LB膜的制备及结构表征

酞菁类化合物具有良好的热稳定性和化学稳定性,已被广泛应用于光敏,气敏,及分子电子器件等领域。用LB方法对酞菁类化合物进行分子组装,用光谱等手段对其膜结构进行表征已引起人们的重视。本文作者之一合成了具有良好LB成膜特性的四(2,4-二特戊基苯     

酞菁铜化合物LB膜的制备及结构形态研究

利用LB技术研究了带有4个长碳氢链的酞菁铜化合物(CuC12Pc)的单分子膜及它与十八胺(ODA)、二十酸(AA)的混合LB膜的聚集结构形态. 结果表明这种酞菁铜化合物在气液界面上可以形成比较稳定有序的双层Langmuir膜, 且可以转移质量较好的多层LB膜. 利用原子力显微镜(AFM)研究了酞菁铜分子的聚集体结构, 发现CuC12Pc/AA混合膜表现为网状的聚集结构, 而CuC12Pc/ODA混合膜形成长岛颗粒状聚集, 并结合UV-Vis吸收光谱讨论了酞菁铜分子形成不同聚集结构的原因.     

Thin-film transistors based on Langmuir-Blodgett films of heteroleptic bis(phthalocyaninato) rare earth complexes

An ordered molecular assembly of heteroleptic bis(phthalocyaninato) rare earth complexes M(Pc)[Pc(OC8H17)8] [M = Tb, Lu; H2Pc = phthalocyanine; H2Pc(OC8H17)8 = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] has been fabricated by the Langmuir-Blodgett (LB) technique and characterized by surface pressure-area isotherms, electronic absorption and polarized electronic absorption spectroscopy, low-angle X-ray diffraction, and atomic force microscopy. The molecular ordering in the LB multilayer film on SiO2 substrate was made into a p-channel field effect transistor (FET), which was generally operated in the enhanced mode. The energy levels of the highest occupied molecular orbital and the lowest unoccupied molecular orbital as well as the energy band diagram can be deduced from the electrochemical measurement results. The charge mobilities of Tb(Pc)[Pc(OC8H17)8] and Lu(Pc)[Pc(OC8H17)8] were calculated to be about 6.4 x 10(-4) and 1.7 x 10(-3) cm2 V(-1) s(-1), respectively.     

Molecules of synthesized phthalocyanine as a material for the detection of 2,4-toluene diisocyanate (TDI)

Various numbers of LB monolayers of a metal-free phthalocyanine derivative, A410H₂Pc, have been deposited onto ultrasonically cleaned quartz substrates with platinum interdigitated electrodes. Similar devices i.e. those with the same number of LB layers, show the same response characteristics in the presence of 35 ppb (0.035 ppm) toluene diisocyanate (TDI)—a toxic substance used in the production of plastics and found in certain types of paint. The response times of the LB devices studied so far have been calculated to be about 40s. The electrical properties of evaporated films of a metal-free phthalocyanine derivative, α-H₂Pc, and those of the A410H₂Pc LB films have been found to be similar. The response time for the evaporated films has been found to be much less that that for the LB films. Although a direct comparison cannot be made between the LB and evaporated films, in this case, results suggest that devices fabricated from evaporated films will be much faster at detecting the presence of TDI than devices fabricated from LB films.     

A New Method of Photopatterning with LB Films Based on a Chemically Amplified Mechanism

IntroductionDeep-UV lithography is generally recognized asthe most promising lithographic technology, for the pro-duction of high-resolution devices. However, lithogra-phy requires high sensitivity, high resolution, and highresistance. To make this techno…     

Synthesis,characterization, and electrical properties of a diazodiphenylene‐bridged Cu–phthalocyanine polymer

A diazodiphenylene‐bridged Cu–phthalocyanine polymer was synthesized from the diazonium salt of bensidine and the Cu(II) 1,8,15,22‐tetraaminophthalocyanine complex and characterized with Fourier transform infrared, ultraviolet–visible spectroscopy, and elemental analysis. The polymer was partially soluble in organic solvents such as dimethylformamide and tetrahydrofuran. The molecular weight of the soluble part of the polymer was investigated with ebullioscopy and viscosimetry methods in tetrahydrofuran. Both methods showed that the molecular weight of the polymer was much larger than that of the complex. The conductivity of the samples was measured with a four‐prop conductivity measuring device. Iodine and hydrogen chloride were doped to the polymer, and an increase of about 10⁴ S cm^?1 in the electrical conductivity was observed. The cyclic voltammogram of the diazodiphenylene‐bridged Cu–phthalocyanine polymer in contact with a LiClO₄ electrolyte exhibited two reductions and two reoxidations with high reversibility and electrochemical stability. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5692–5698, 2006     

Syntheses,crystal, molecular structures,and solution studies of Cu(II), Co(II), and Zn(II) coordination compounds containing pyridine-2,6-dicarboxylic acid and 1,4-pyrazine-2,3-dicarboxylic acid: comparative computational studies of Cu(II) and Zn(II) complexes

Structural Chemistry - Three new coordination compounds of Cu(II), Co(II), and Zn(II) based on different dicarboxylic acids formulated as (AcrH)[Cu(pydc)(pydcH)]·5H2O (1)...     

PREPARATION AND PROPERTIES OF TETRA (p-VINYLPHENOXY) METALLOPHTHALOCYANINES

This paper describes the preparation and Langmuir-Blodgett (LB) monomolecular film formation of H_2, Cu, Ni, Co, and Zn phthaloeyanine compounds with p-vinyiphenoxy peripheral substituent on each benzo ring at either 2- or 3- position [i.e., tetra (p-vinylphenoxy) substituted isomer mixture]. These phthalocyanine derivatives form stable LB films at the film pressures greater than 10 dynes/cm. The surface pressure-area isotherms indicate that the phthalocyanine units are densely packed with a eofacial orientation. Schottky cells of [Indium-Tin Oxide/LB film/Al] were prepared and their electronic properties were examined. Much better rectifying properties, diode parameter, break-down potential and mechanical strength were notified by the post-polymerization of LB-layers. On exposing the polymerized films to tetrahydrofuran vapor, the absorption maxima of Q-band shift bathochromically by about 100 nm, being sensitive to diode laser light.     

Methyloxy Substituted Heteroleptic Bis(phthalocyaninato) Yttrium Complexes: Density Functional Calculations

The effects of alkyloxy substituents attached to one phthalocyanine ligand of three heteroleptic bis(phthalocyaninato) yttrium complexes Y(Pc)[Pc(α‐OCH₃)₄] ( 1 ), Y(Pc)[Pc(α‐OCH₃)₈] ( 2 ), and Y(Pc)[Pc(β‐OCH₃)₈] ( 3 ), as well as their reduction products {Y(Pc)[Pc(α‐OCH₃)₄]}^? ( 4 ), {Y(Pc)[Pc(α‐OCH₃)₈]}^? ( 5 ), and {Y(Pc)[Pc(β‐OCH₃)₈]}^? ( 6 ) [H₂Pc(α‐OCH₃)₄=1,8,15,22‐tetrakis(methyloxy)phthalocyanine; H₂Pc(α‐OCH₃)₈=1,4,8,11,15,18,22,25‐octakis(methyloxy)phthalocyanine; H₂Pc(β‐OCH₃)₈=2,3,9,10,16,17,23,24‐octakis(methyloxy)phthalocyanine] are studied by DFT calculations. Good consistency is found between the calculated results and experimental data for the electronic absorption, IR, and Raman spectra of 1 and 3 . Introduction of electron‐donating methyloxy groups on one phthalocyanine ring of the heteroleptic double‐deckers induces structural deformation in both phthalocyanine ligands, electron transfer between the two phthalocyanine rings, changes in orbital energy and composition, shift of electronic absorption bands, and different vibrational modes of the unsubstituted and substituted phthalocyanine ligands in the IR and Raman spectra in comparison with the unsubstituted homoleptic counterpart Y(Pc)₂. The calculations reveal that incorporation of methyloxy substituents at the nonperipheral positions has greater influence on the structure and spectroscopic properties of bis(phthalocyaninato) yttrium double‐deckers than at the peripheral positions, which increases with increasing number of substituents. Nevertheless, the substituent effect of alkyloxy substituents at one phthalocyanine ligand of the double‐decker on the unsubstituted phthalocyanine ring and on the whole molecule and the importance of the position and number of alkyloxy substituents are discussed. In addition, the effect of reducing 1 – 3 to 4 – 6 on the structure and spectroscopic properties of the bis(phthalocyaninato) yttrium compounds is also discussed. This systemic DFT study is not only useful for understanding the structure and spectroscopic properties of bis(phthalocyaninato) rare earth metal complexes but also helpful in designing and preparing double‐deckers with tunable structure and properties.     

Exploiting distinct molecular architectures of ultrathin films made with iron phthalocyanine for sensing

The possibility of generating distinct film properties from the same material is crucial for a number of applications, which can only be achieved by controlling the molecular architecture. In this paper we demonstrate as a proof-of-principle that ultrathin films produced from iron phthalocyanine (FePc) may be used to detect trace amounts of copper ions in water, where advantage was taken of the cross sensitivity of the sensing units that displayed distinct electrical properties. The ultrathin films were fabricated with three methods, namely physical vapor deposition (PVD), Langmuir-Blodgett (LB), and electrostatic layer-by-layer (LbL) techniques, where for the latter tetrasulfonated phthalocyanine was used (FeTsPc). PVD and LB films were more homogeneous than the LbL films at both microscopic and nanoscopic scales, according to results from micro-Raman spectroscopy and atomic force microscopy (AFM), respectively. From FTIR spectroscopy data, these more homogeneous films were found to have FePc molecules oriented preferentially, tilted in relation to the substrate surface, while FeTsPc molecules were isotropically distributed in the LbL films. Impedance spectroscopy measurements with films adsorbed onto interdigitated gold electrodes indicated that the electrical response depends on the type of film-forming method and varies with incorporation of copper ions in aqueous solutions. Using principal component analysis (PCA), we were able to exploit the cross sensitivity of the sensing units and detect copper ions (Cu(2+)) down to 0.2 mg/L, not only in ultrapure water but also in distilled and tap water. This level of sensitivity is sufficient for quality control of water for human consumption, with a fast, low-cost method.     

新型两亲性酞菁锌LB膜的研究

本文合成了一种新型的两亲性酞菁分子,研究了它在不同溶剂中的聚集行为,考察了酞菁及酞菁与正十六烷混合的成膜性能,制备了混合的多层LB膜,并利用紫外光谱研究LB膜内的分子聚集状况,用分子激子理论对实验结果加以分析,还应用偏振紫外的方法对LB膜内酞菁分子大环的取向进行了确定。     

Inhibitorial effect of the Cu(II) and Ni(II) complexes with polyamines and imidazole derivatives on the Ca,Mg-dependent ATP-ase substrate

The investigation of the inhibitory activity on the Ca,Mg-dependent ATP-ase substrate of some Cu(II) and Ni(II) complexes with polyamines and imidazole derivatives is reported. These results show that the Cu(II) complexes have high inhibitorial effect with the exception of the following very stable compounds: square planar [Cu(N-PropIm)₂(NCS)₂], distorted octahedral [Cu(bipy)₂(NCS)₂] and five coordinate [Cu(Me₆tren)(NCS)] (SCN). The Ni(II) derivatives present a medium inhibitorial activity except to the stable tetrahedral [Ni(N-PropIm)₂(NCS)₂], hexacoordinate [Ni(dpt)(tn)(NCS)] (SCN) and fivecoordinate [Ni(dpt)(tn)]Br₂ and [Ni(Me₆tren)(NCS)] (SCN). An explanation of these conclusions is reported.     

新型LB成膜材料-两亲性侧链取代酞菁锌的合成

本文合成了一种新型的两亲性硬脂酸侧链取代的酞菁化合物, 利用LB膜技术制备了酞菁化合物与正十六烷混合的单层和多层LB膜, LB膜内酞菁分子大环与基片大体平行, 表明该分子具有良好的成膜性能。     

Synthesis,Characterization and Structure of Bis‐ and Tetrakis‐Aziridine‐Nickel(II) and Copper(II) Complexes

The synthesis and characterization of mononuclear tetrakis‐aziridine nickel(II ) and copper(II ) complexes as well as of a dinuclear bis‐aziridine copper(II ) complex are described. The reactions of anhydrous MCl₂ (M = Ni^II, Cu^II) with aziridine (= az = C₂H₄NH, C₂H₃MeNH, CH₂CMe₂NH) in CH₂Cl₂ at room temperature in a 1:5 and 1:2 molar ratio, respectively, afforded the tetrakis‐aziridine complexes [M(az)₄Cl₂] (M = Ni, Cu) or the dimeric bis‐aziridine complex [Cu(az)₂Cl₂]₂. After purification, all of the complexes were fully characterized. The single crystal structure analysis revealed two different coordination modes. Whereas both nickel(II ) complexes can be classified as showing an elongated octahedral structure, copper(II ) complexes show either an elongated octahedral or a square pyramidal arrangement forming dimers with chlorido bridges in axial positions. Furthermore, the results of magnetic measurements of the nickel(II ) and copper(II ) compounds are presented.     

Copper(I)-mediated radical polymerization of methacrylates in aqueous solution

α-Methoxypolyethylene oxide methacrylate was polymerized by copper(I)-mediated living radical polymerization in aqueous solution to give polymers with controlled number-average molecular masses and narrow polydispersities. When equimolar quantities of initiator with respect to copper(I) bromide were used, the reaction was extremely fast with quantitative conversion achieved in less than 5 min at ambient temperature. However, the molecular weight distribution was broad, and control over the number-average molecular weight (M_n) growth was extremely poor; this is ascribed to an increase in termination because of the increased rate as a result of the coordination of water at the copper center. The complex formed between copper(I) bromide and N-(n-propyl)-2-pyridylmethanimine, bis[N-(n-propyl)-2-pyridylmethanimine]copper(I), was demonstrated to be stable in aqueous solution by ¹H NMR over 10 h at 25 °C. However, on increasing the temperature to 50 °C, decomposition occurred rapidly. Thus, polymerization temperatures were maintained at ambient temperature. When longer alkyl chains were utilized in the ligand, that is, pentyl and octyl, the complex acted as a surfactant leading to heterogeneous solutions. When the catalyst concentration was reduced by two orders of magnitude, the rate of polymerization was reduced with 100% conversion achieved after 60 min with the M_n of the final product being higher than that predicted and the polydispersity equal to 1.43. Copper(II) was added as an inhibitor to circumvent these problems. When 10% of Cu(I) was replaced by Cu(II) {[Cu(I)] + [Cu(II)]/[I] = 1/100}, the mass distribution showed a bimodal distribution, and the rate of polymerization decreased significantly. With a catalyst composition [Cu(I)]/[Cu(II)] = 0.5/0.5 {[Cu(I)] + [Cu(II)]}/[I] = 1/100, polymerization proceeded slowly with 80% conversion reached after 22 h. Thus, the concentration of Cu(I) was further reduced with [Cu(I)]/[Cu(II)] = 10/90, {[Cu(I)] + [Cu(II)]}/[I] = 1/100. The system then contained [Initiator]/[Cu(I)] = 1000/1 and [I]/[Cu(II)] = 1000/9. Under these conditions, the reaction reached 50% after 5 h with the polymer having both an M_n close to the theoretical value and a narrow polydispersity of PDi = 1.15. Optimum results were obtained by increasing the amount of catalyst. When a ratio of [Cu(I)]/[Cu(II)] = 10/90 with a ratio of [Cu]/[I] = 1/1, a conversion of 100% was achieved after less than 20 h, leading to a product having M_n = 8500 and PDi = 1.15. Decreasing the amount of Cu(II) relative to Cu(I) to [Cu(I)]/[Cu(II)] = 0.5/0.5 (maintaining the overall amount of copper) led to 100% conversion after 75 min: M_n = 9500, PDi = 1.10. Block copolymers have been demonstrated by sequential monomer addition with excellent control over M_n and PDi. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1696–1707, 2001     

[CuCl3(H2O)]− complexes aggregated to form hydrate columns in methyl‐substituted pyridinium or piperidinium salts

1,2,3‐Trimethylpyridinium aquatrichloridocuprate(II), (C₈H₁₂N)[CuCl₃(H₂O)], (I), 3,4‐dimethylpyridinium aquatrichloridocuprate(II), (C₇H₁₀N)[CuCl₃(H₂O)], (II), and 2,3‐dimethylpyridinium aquatrichloridocuprate(II), (C₇H₁₀N)[CuCl₃(H₂O)], (III), exhibit the same fundamental structure, with (I) and (II) isomorphous and with the unit‐cell constants of (III) similar to the reduced unit‐cell constants of (I) and (II). The distorted square‐planar [CuCl₃(H₂O)]⁻ complex [mirror symmetric in (I) and (II)] forms two semicoordinate Cu...Cl bonds to a neighboring complex to produce a dimer with 2/m symmetry [only inversion symmetry in (III)]. The semicoordinate Cu...Cl bond length of the dimer shows significant elongation at 295 K compared with that at 100 K, while the coordinate Cu—Cl bond lengths are slightly contracted at 295 K compared with those at 100 K. The inorganic dimers are linked by eight hydrogen bonds to four neighboring dimers to establish a checkerboard network layer in the ab plane, with voids between the dimers that accommodate, on both sides, inversion‐related organic cation pairs. The organic cations are required by mirror‐plane symmetry to be disordered in (I) and (II). The organic cations and [CuCl₃(H₂O)]⁻ complexes are nearly coplanar and tilted out of the layer plane to establish a hybrid organic–inorganic layer structure parallel to (202) [(11) in (III)], with hydrate columns (defined by water molecules) and hydrophobic columns (defined by methyl groups) parallel to each other [and along the 2₁ axes in (I) and (II)]. In 1,1‐dimethylpiperidinium aquatrichloridocuprate(II), (C₇H₁₆N)[CuCl₃(H₂O)], (IV), the bulkier organic cation prevents semicoordinate bonding between complexes, which are hydrogen bonded side‐to‐side in zigzag chains that place water molecules in columns along half of the 2₁ axes.     

Synthesis, characterization, solution study and crystal structure of complexes of Cr(III), Co(II), Ni(II) and Cu(II) with chelidamic acid and 2,9-dimethyl-1,10-phenanthroline

The title compounds, (dmpH)[Cr(chelH)₂]·3H₂O, 1, (dmpH)[Co(chelH₂)(chelH)]·3H₂O, 2, (dmpH)[Ni(chelH₂)(chelH)]·2H₂O, 3 and [Cu(chelH)(dmp)]·3H₂O, 4 (dmp is 2,9-dimethyl-1,10-phenanthroline and chelH₃ is chelidamic acid or 4-hydroxypyridine-2,6-dicarboxylic acid) were obtained by one-pot reaction of 2,9-dimethyl-1,10-phenanthroline and 4-hydroxypyridine-2,6-dicarboxylic acid with corresponding salts in aqueous solution. The compounds were identified by IR, MS, elemental analysis and single crystal X-ray crystallography; also they were studied in the solution phase. The compounds 1, 2 and 3 are similar in coordination sphere around the metal ions, with some differences between protonation sites of chelidamate ion and the charge of complex, but compound 4 is essentially different. The compounds 1, 2 and 3 are six coordinated, but 4 is five coordinated. There are various O–H···O, O–H···N and N–H···O hydrogen bonds found in the structures. In a solution study, the protonation constants of dmp and chel, the equilibrium constants of the chel–dmp proton-transfer system and the stoichiometry and stability of complexation of this system with Cr(III), Co(II), Ni(II) and Cu(II) ions in an aqueous solution were investigated by potentiometric pH titration method. The stoichiometry of the most complexes species in solution was found to be very similar to the crystalline cited metal ion complexes.     

Phosphorus‐nitrogen compounds. Part 39. Syntheses and Langmuir‐Blodgett thin films and antimicrobial activities of N/N and N/O spirocyclotriphosphazenes with monoferrocenyl pendant arm

The Cl substitution reactions of the N/N ( 1 ‐ 3 ) and N/O ( 4 and 5 ) spirocyclic monoferrocenylphosphazenes with 1,4‐dioxa‐8‐azaspiro[4,5]decane (DASD) produce the mono‐ ( 1a ‐ 5a ), geminal‐ ( 1b ‐ 5b ) and tetrakis‐DASD‐substituted ferrocenylspirocyclotriphosphazenes ( 1c ‐ 5c ). The mono‐ and geminal‐DASD‐substituted phosphazenes have two and one stereogenic P‐centers, respectively. The structures of the compounds were established by spectroscopic techniques. The molecular structures of 3a and 2b were evaluated using X‐ray crystallography. Additionally, the ultrathin and highly ordered Langmuir‐Blodgett (LB) films of 3a and 2b were also prepared. The characterizations of the LB films were done using p‐polarized grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques. On the other hand, the antimicrobial activities of the eight phosphazene derivatives against G(+) and G(‐) bacteria and fungi were investigated. Furthermore, the interactions between the compounds and plasmid DNA were studied by agarose gel electrophoresis.     

Preparation, luminescence and photoelectric properties of Langmuir-Blodgett films of alkynylplatinum(II)-zinc(II) porphyrinate/heteropolyoxometalate hybrid composites

A new class of organometallic/inorganic hybrid Langmuir-Blodgett (LB) films, consisting of rigid-rod alkynylplatinum(II)-zinc(II) porphyrinate complex (OMA) as the π-conjugated donor-acceptor-type molecule and tungsto(molybdo)phosphoric heteropolyacids (HPA) (HPA = H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀, abbreviated as HPMo₁₂ and HPW₁₂, respectively) of the Keggin structure as the inorganic component, were prepared and characterized by π-A isotherms, UV-vis absorption and luminescence spectra, low-angle X-ray diffraction, scanning tunneling microscopy and surface photovoltage spectroscopy. Our experimental results indicate that stable, well-defined and well-organized Langmuir and LB films have been formed in pure water and heteropolyacid subphase. They typically have a highly organized lamellar structure in which a monolayer of HPA is most likely embedded inside the OMA molecular space formed by long chains of PBu₃. Luminescence spectra of these hybrid LB films show that HPMo₁₂ and HPW₁₂ can enhance the emission of OMA to some extent. These LB composites show good photovoltage responses and a photovoltage of 79 μV can be obtained for the OMA/HPMo₁₂ system when it is excited by light. The monolayer LB films on ITO wafer can also display interesting electrical conductivity.     

Synthesis and genotoxicity of Schiff base transition metal complexes

A new ONNO‐type azomethine ligand, 2,2′‐(ethane‐1,2‐diylidenedinitrilo)dibenzoic acid, (YLH₂) ( 1 ) has been prepared by the condensation of 2‐aminobenzoic acid and glyoxal. The coordination compounds [Ni(YL)] ( 2 ), [Co(YL)] ( 3 ), [Cu(YL)(H₂O)] ( 4 ), [Zn(YL)] ( 5 ), and [Cd(YL)] ( 6 ) of the YLH₂ ligand with five transition metal ions, Ni(II) Co(II), Cu(II), Zn(II), and Cd(II) have been prepared. The structures of these new azomethine compounds are proposed on the basis of the elemental analyses, proton nuclear magnetic resonance, infrared, ultraviolet–visible spectroscopy, and X‐ray powder diffraction patterns. Elemental analyses indicate a ligand metal ratio of 1:1 in the coordination compounds. X‐ray powder diffraction parameters for [Cu(YL)(H₂O)] and [Cd(YL)] compounds correspond to orthorhombic and monoclinic structures, respectively. The ligand acts as a tetradentate ligand bending through oxygen atoms of the hydroxyl groups of benzoic acid and nitrogen atoms of the azomethine groups. In addition, the ligand and its metal complexes have been studied for their possible genotoxic potential. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:119–130, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20665