Unsymmetrical phthalocyanines with alkynyl substituents

The synthesis of unsymmetrically substituted metallophthalocyanines (M = Zn, Ni, Co) bearing two phenylethyl moieties and six alkythio substituents was achieved by co-cyclotetramerization of two different phthalonitrile derivatives, namely 4,5-di(hexylthio)phthalonitrile and 4,5-di(phenylethynyl)phthalonitrile in the presence of zinc, cobalt or nickel salts. In contrast to the totally alkyne substituted phthalocyanines, these partially alkyne-containing derivatives are more soluble and their Q band absorptions are red-shifted when compared with all alkylthio phthalocyanines. Electrochemical properties of the phthalocyanines were studied by cyclic voltammetry.     

Synthesis and characterization of a novel series of unsymmetrical porphyrins

A novel series of unsymmetrical porphyrins with aldehyde group at the terminal of the linkage which connected to meso-phenyl through acylamide bond have been synthesized and structurally characterized by IR,~1H NMR,MS,UV-vis,fluorescence.     

Synthesis,electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric characterization of new phthalocyanines peripherally fused to four flexible crown ether moieties

Novel Ni(II), Zn(II), Co(II) and Cu(II) phthalocyanines with four peripheral 4-[methyleneoxy(18-crown-6)] groups have been synthesized via the cyclic tetramerization of 4-[{(18-crown-6)-yl}methyleneoxy]phthalonitrile and the corresponding metal salts (NiCl₂, Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The thermal stabilities of the metal-free and metallophthalocyanine compounds were determined by thermogravimetric analysis. The structures of the target compounds were confirmed using elemental analysis, IR, ¹H-NMR, ¹³C-NMR, UV–Vis and MS spectral data. Voltammetric and in situ spectroelectrochemical measurements show that while the cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, the metal-free, nickel, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. An in situ electrocolorimetric method has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes.     

Synthesis, spectroscopic and electrochemical property of an unsymmetrical porphyrin and its Zn compound

<正>In this article,a new 5-(p-maleicaminophenyl)-10,15,20-triphenylporphyrin(H_2P) and relative zinc compound(ZnP) were synthesized and characterized by means of elemental analyses,UV-vis,IR,MS and ~1H NMR spectroscopies.Furthermore,we have investigated the fluorescence spectroscopy of these compounds.The oxidation and reduction properties of the compounds were studied by the cyclic voltarnmetry,the oxidation-reduction potentials were obtained.     

Synthesis,characterization and electrochemistry of a new organosoluble metal-free and metallophthalocyanines

4-[2-(Phenylthio)ethoxy]phthalonitrile 3 was synthesized by nucleophilic displacement of nitro group in 4-nitrophthalonitrile with 2-(phenylthio)ethanol 1. The metal-free phthalocyanine 4 was prepared by the reaction of a dinitrile monomer with 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I) phthalocyanines 5, 7, 8 were prepared by reaction of the dinitrile compound with the chlorides of Ni(II), Co(II), Cu(I) in DMAE. Zn(II) phthalocyanine 6, was prepared by reaction of the dinitrile compound with the acetates of Zn(II) in DMAE. Electrochemical behaviours of novel metal-free, Co(II) and Zn(II) phthalocyanines were investigated by cyclic voltammetry, potential differential pulse voltammetry techniques. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis and MS spectral data.     

Novel phthalocyanines bearing four 4-phenyloxyacetic acid functionalities

Metal-free (2) and Co(II), Zn(II), Ni(II), Cu(II) metallophthalocyanines (2a–d) with four 4-phenyloxyacetic acid groups on the periphery were prepared by cyclotetramerization of new p-(3,4-dicyanophenoxy)phenylacetic acid (1) and the corresponding divalent metal salts. Further reactions of these products with thionylchloride and then benzylamine in tetrahydrofuran, and octanol in pyridine gave amide (3, 3a–d) and ester (4, 4a–d) derivatives, respectively. The new compounds have been characterized by elemental analyses, IR, UV–Vis, mass and ¹H NMR spectroscopy. The redox properties of compounds 2 and 2a–d were identified by cyclic voltammetry.     

Synthesis and electrochemical characterization of biphenyl-malonic ester substituted cobalt,copper, and palladium phthalocyanines

Phthalocyanines with four biphenyl-malonic ester groups on the periphery were synthesized by cyclotetramerization of 4-(1,1-dicarbethoxy-2-(4-biphenyl)-ethyl)-phthalonitrile. The new compounds were characterized by elemental analyses, FT-IR, ¹H NMR, ¹³C NMR, UV–Vis, and MASS spectral data. Electrochemical behaviors of novel Co(II), Cu(II), and Pd(II) phthalocyanines were investigated by cyclic voltammetry, potential differential pulse voltammetry, and applied potential chronocoulometry techniques. While Cu(II) and Pd(II) phthalocyanines give up to four common phthalocyanine ring reductions, Co(II) phthalocyanine gave two ligand-centered and two metal-centered redox processes. HOMO–LUMO gap of the complexes are comparable with the reported MPc papers.     

Synthesis and electrochemical properties of crown ether functionalized coumarin substituted cobalt and copper phthalocyanines

The synthesis of novel 6,7-[15-crown-5]-3-[p-(3,4-dicyanophenoxy)phenyl]coumarin (1)/6,7-[15-crown-5]-3-[p-(2,3-dicyanophenoxy)phenyl]coumarin (2) and their peripherally/non-peripherally cobalt and copper phthalocyanine complexes (3-6) have been prepared and characterized by elementel analysis, ¹H-NMR, MALDI-TOF, FT-IR and UV-Vis spectral data. Fluorescence intensity changes of compound 1 and 2 have been determined by addition of Na⁺ or K⁺ ions at 25 °C in THF. The effect of substitution type on the redox and aggregation behaviour of the compounds was investigated by voltammetry and in situ spectroelectrochemistry.     

Characterizations and thermal stability of soluble polyimide derived from novel unsymmetrical diamine monomers

Two kinds of novel aromatic, unsymmetrical diamines with ether-ketone group, 3-amino-4′-(4-amino-2-trifluoromethylphenoxy)-benzophenone and 3-amino-4′-(4-aminophenoxy)-benzophenone, was successfully synthesized by two different synthetical routes and polymerized with various aromatic tetracarboxylic acid dianhydrides, including 4,4′-oxydiphthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, and 2,2′-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride, via a conventional two-step thermal or chemical imidization method to produce a series of fluorinated polyimides. The polyimides were characterized with solubility tests, viscosity measurements, mechanical properties tests, IR-FT, and thermogravimetric analysis. The polyimides had inherent viscosities of 0.54-0.77 dL/g and were easily dissolved in both polar, aprotic solvents and common, low-boiling-point solvents. The resulting strong and flexible polyimide films exhibited excellent thermal stability, with decomposition temperatures (at 10% weight loss) above 573 °C and glass-transition temperatures in the range of 222-251 °C. Moreover, the polymer films showed outstanding mechanical properties, with tensile strengths of 86.5-121.6 MPa, elongations at break of 9-16%, and initial moduli of 1.26-1.97 GPa. These outstanding combined features ensure that the polymers are desirable candidate materials for advanced applications.     

Synthesis and antimycotic activity of new unsymmetrical substituted zinc phthalocyanines

The synthesis of new unsymmetrical substituted zinc phthalocyanines derivatives has been described; moreover the photodynamic activity of some compounds tested against Candida albicans has been reported.     

Synthesis, photophysical and thermal studies of symmetrical and unsymmetrical zinc phthalocyanines

The novel zinc phthalocyanine (3) with malonylester and chloro groups on each benzo unit was synthesized from 4-diethoxymalonyl-5-chloro-phthalonitrile (1). The unsymmetrically substituted zinc phthalocyanine (5), carrying hexylthio, malonylester and chloro groups at the periphery, was obtained from 4-diethoxymalonyl-5-chloro-phthalonitrile (1) and 4,5-bis-hexylsulfanyl-phthalonitrile (2) by a statistical condensation method as an A₃B type unsymmetrical phthalocyanine compound. Transesterification of the malonyl esters of the new symmetrical and unsymmetrical phthalocyanines occurred during the cyclotetramerization of dinitriles with Zn(CH₃COO)₂ in 1-pentanol in the presence of DBU. Octa-hexylthio-substituted zinc phthalocyanine (4) was prepared according to the literature. The photophysical and thermal properties of all the phthalocyanine complexes are described for the first time. These novel symmetrical and unsymmetrical phthalocyanine macrocycles have been characterized by a series of spectroscopic methods including ¹H NMR, electronic absorption, IR and mass spectroscopy, in addition to elemental analysis. Their narrow long wavelength absorption band shows that the bulky substituents on the periphery prevent aggregation. The unsymmetrically substituted phthalocyanine (5) gave a greater fluorescence quantum yield in chloroform than the symmetrical analogues (3 and 4).     

Comparative electrooxidation of nitrite by electrodeposited Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines on gold electrodes

This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1-1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM⁻¹ were observed for all the modified electrodes.     

Synthesis of novel redox calix[4]arene derivative with 1,3-substituted large conjugated ferrocene bridge

A novel redox calix[4]arene derivative with 1,3-substituted large conjugated ferrocene bridge was designed and synthesized in high yield.Its structure was characterized by element analysis,IR,ESI-MS,NMR spectrum,etc.The primary study of cyclic voltammetry showed it possessed excellent reversible electrochemistry response property.     

Synthesis of new phthalocyanines substituted with four benzo[d]thiazol-2-ylthio groups

The synthesis of a new phthalonitrile derivative (4-(benzo[d]thiazol-2-ylthio)phthalonitrile), its metal-free phthalocyanine, and metallo-phthalocyanines are described. Phthalocyanines are formed in high yield with template synthesis. These compounds showed considerable solubility in CHCl₃, DMF and DMSO, a primary condition for potential applications. The newly synthesized compounds have been characterized by elemental analyses, UV-Visible spectra, IR and ¹H-NMR.     

Synthesis and characterization of fluorinated polyimides derived from novel unsymmetrical diamines

Two kinds of aromatic, unsymmetrical diamines with ether-ketone group, 3-amino-4′-(4-amino-2-trifluoromethylphenoxy)-benzophenone and 4-amino-4′-(4-amino-2-trifluoromethylphenoxy)-benzophenone, were successfully synthesized with two different synthetic routes. Then, they were polymerized with 4,4′-oxydiphthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, and 2,2′-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride to form a series of fluorinated polyimides via a conventional two-step thermal or chemical imidization method. The resulting polyimides were characterized by measuring their solubility, viscosity, mechanical properties, IR-FT, and thermal analysis. The results showed that the polyimides had inherent viscosities of 0.48-0.68 dl/g and were easily dissolved in bipolarity solvents and common, low-boiling point solvents. Meanwhile, the resulting strong and flexible polyimide films exhibited excellent thermal stability, e.g., decomposition temperatures (at 10% weight loss) are above 575 °C and glass-transition temperatures in the range of 218-242 °C. The polymer films also showed outstanding mechanical properties, such as tensile strengths of 86.5-132.8 MPa, elongations at break of 8-14%, and initial moduli of 1.32-1.97 GPa. These outstanding combined features ensure that the polymers are desirable candidate materials for advanced applications.     

Synthesis of unsymmetrical 4,6-diarylpyrimidines

Unsymmetrical 4,6-diarylpyrimidines were synthesized using Suzuki coupling reaction via selective arylation of 4,6-dichloropyrimidine.     

Synthesis,electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric characterization of new metal-free and metallophthalocyanines substituted with 4-{2-[2-(1-naphthyloxy)ethoxy]ethoxy} groups

The synthesis of novel metal-free and metallophthalocyanines [Ni(II), Zn(II), Co(II), Cu(II)] were prepared by cyclotetramerization of a novel 4-{2-[2-(1-naphthyloxy)ethoxy]ethoxy}phthalonitrile and the corresponding metal salts (NiCl₂, Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The structures of the target compounds were confirmed using elemental analysis, IR, ¹H NMR, ¹³C NMR, UV–Vis and MS spectral data. Voltammetric and in situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, metal-free, and zinc phthalocyanines show only ring-based reduction and oxidation processes. All complexes decomposed and coated on the electrode as nonconductive film at positive potential window of the electrolyte. An in situ electrocolorimetric method has been applied to investigate color of the electro-generated anionic and cationic forms of the complexes.     

Synthesis and electrochemical behavior of novel peripherally and non-peripherally substituted ball-type cobalt phthalocyanine complexes

The syntheses of new ball-type Co(II) phthalocyanines containing 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at non-peripheral (complex 6) and peripheral (complex 7) positions are presented. These complexes were characterized by UV-Vis, FT-IR, mass spectroscopy and electrochemical methods. Both complexes exhibit metal and ring based redox processes, typical of cobalt phthalocyanine complexes. For 6, the metal based reduction was observed at −0.46 V followed by a ring based reduction at −1.40 V. The metal oxidation for 6 was observed at +0.16 V and the ring based oxidation at +1.05 V. For 7, reductions are easier but the oxidations are more difficult. The metal based reduction for 7 was observed at −0.38 V followed by a ring based reduction at −1.03 V. The metal oxidation for 7 was observed at +0.20 V and the ring based oxidation at +1.35 V.     

Study on synthesis and properties of poly(ferrocenylbutylmethylsilane) with unsymmetrical silicon substitution groups

Novel poly(ferrocenylⁿbutylmethylsilane) with unsymmetrical silicon substitution groups [Fe(η-C₅H₄)₂(SiBuMe)]_n (PFBMS) (6) have been prepared via the thermal ring-opening polymerization (ROP) of the corresponding strained silicon-bridge [1] ferrocenophanes [Fe(η-C₅H₄)₂(SiBuMe)] (4) and via the nucleophilic substitution of poly(ferrocenylmethylchlorosilane) [Fe(η-C₅H₄)₂(SiMeCl)]_n (5) with n-butyllithium. Resultant PFBMS was structurally characterized by ¹H NMR and UV/visible spectroscopy. The molecular weights of PFBMS (6) were measured by gel permeation chromatography (GPC) using polystyrene standard, and the solution electrochemical behavior of PFBMS was investigated by cyclic voltammetry (CV).     

Synthesis of novel push-pull unsymmetrically substituted alkynyl phthalocyanines

Two families of "push-pull" phthalocyanines 1-3 having an unusually strong dipole moment have been prepared. The syntheses of unsymmetrically substituted phthalocyanines 1a,b and 2 bearing one or two electron-withdrawing 4-nitrophenylethynyl moieties, respectively, and six alkoxy substituents were performed by combination of a zinc or nickel templated cyclotetramerization and cross-coupling palladium mediated methodologies. In a similar way, the "push-pull" compounds 3a,b having a reversal substitution pattern, characterized by the presence of one electron-donor 4-(dimethylamino)phenylethynyl unit and six strong acceptor alkylsulfonyl substituents were prepared. The compounds show very large second-order nonlinear optical responses.