Phthalocyanine polymers. IV. Novel type of thermally stable polyimides derived from metal phthalocyanine tetramines and benzophenone tetracarboxylic dianhydride

Poly(metal phthalocyanine)imides of copper, cobalt, nickel, and zinc were synthesized by the reaction of metal phthalocyanino tetramines with benzophenone tetracarboxylic dianhydride. These polymers were characterized by elemental analyses and IR, TGA, and inherent viscosity studies. Noteworthy features of these phthalocyanine polymers are their remarkable thermal and thermooxidative stabilities with char yields at 800°C that range from 78 to 83% in a nitrogen atmosphere. The relative thermal stabilities of these polymers have been evaluated by activation energy measurements.     

Synthesis and photophysical studies of phthalocyanine-gold nanoparticle conjugates

This work reports on the synthesis, characterization and photophysical studies of phthalocyanine-gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ～5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.     

Macromolecular Recognition and Macroscopic Interactions by Cyclodextrins

Herein macromolecular recognition by cyclodextrins (CDs) is summarized. Recognition of macromolecules by CDs is classified as main‐chain recognition or side‐chain recognition. We found that CDs form inclusion complexes with various polymers with high selectivity. Polyrotaxanes in which many CDs are entrapped in a polymer chain were prepared. Tubular polymers were prepared from the polyrotaxanes. CDs were found to recognize side‐chains of polymers selectively. CD host polymers were found to form gels with guest polymers in water. These gels showed self‐healing properties. When azobenzene was used as a guest, the gel showed sol‐gel transition by photoirradiation. When ferrocene was used, redox‐responsive gels were obtained. Macroscopic self‐assembly through molecular recognition has been discovered. Photoswitchable gel association and dissociation have been observed.     

Influence of chlorine substitution on the self-assembly of zinc phthalocyanine

The adsorption and ordering of zinc phthalocyanine (ZnPc) and octachloro zinc phthalocyanine (ZnPcCl(8)) on an Ag(111) surface is studied in situ by scanning tunneling microscopy under ultrahigh vacuum. Two-dimensional self-assembled supramolecular domains are observed for these two molecules. We show how substituting chlorine atoms for half of the peripheral hydrogen atoms on ZnPc influences the self-assembly mechanisms. While intermolecular interactions are dominated by van der Waals forces in ZnPc molecular networks, ZnPcCl(8) molecular packing undergoes a sequential phase evolution driven by the creation of C-Cl...H-C hydrogen bonds between adjacent molecules. At the end of this evolution, the final molecular assembly involves all possible hydrogen bonds. Our study also reveals the influence of molecule-substrate interactions through the presence of fault lines generating a stripe structure in the molecular film.     

Phthalocyanine polymers. V. Novel type of thermally stable polyimides derived from metal phthalocyanine tetraamines and pyromellitic dianhydride

New poly(metal phthalocyanine) pyromellitimides of copper, cobalt, nickel, and zinc were synthesized and elemental, IR, TGA, and inherent viscosity measurement studies were done to characterize these polymers. They showed exceptional thermal and thermo-oxidative stability with char yields at 800°C ranging from 75 to 87% in a nitrogen atmosphere. The ratio of the polymer decomposition temperatures in air and nitrogen (PDT) (air)/PDT (N₂) varied from 0.91 to 0.97, which indicated that the onset of degradation of these polymers is greatly affected by the presence of an oxidizing atmosphere. Isothermal studies were done to evaluate the long-term thermal stability of these polymers.     

Photoinduced intramolecular electron transfer and charge separation in zinc phthalocyanine-viologen linked system

Photoinduced electron transfer and charge separation processes in zinc phthalocya-nine-viologen linked system have been studied and the distance effect of donor/acceptor on electron transfer reaction is discussed. It is indicated that the fluorescence from the zinc phthalocyanine moiety is appreciably quenched and the life-time of singlet excited state is reduced by the pendant viologen. Time-resolved transient absorption spectra measurements show that intramolecular quenching of the triplet state of zinc phthalocyanine by the attached viologen results in charge separation giving reduced viologen radical alive for a rather long period with hundred microsecond duration. The effect of the carbon chain length on the electron transfer rate constant and charge separation efficiency suggests that upon excitation, the zinc phthalocyanine and viologen groups tend to take closer conformation with the increase of the carbon chain examined. The rate constant for the intramolecular electron transfer ket with n = 3     

Phenylboronate‐diol crosslinked polymer/SWCNT hybrid gels with reversible sol–gel transition

This work demonstrates the successful incorporation of functionalized single‐walled carbon nanotubes (f‐SWCNTs) into the phenylboronate‐diol crosslinked polymer gel to create a hybrid system with reversible sol–gel transition. The phenylboronic acid‐containing and diol‐containing polymers were first separately prepared by the reversible addition–fragmentation chain transfer polymerization. Covalent functionalization of single‐walled carbon nanotubes (SWCNTs) with an azide‐derivatized, diol‐containing polymer was then accomplished by a nitrene addition reaction. Subsequently, the hybrid gels were prepared by crosslinking the mixture of f‐SWCNTs and diol‐containing polymer with the phenylboronic acid‐containing polymer. The hybrid gel has been characterized by scanning electron microscopy (SEM) and rheological analysis. The SEM measurement demonstrated a homogeneous dispersion of f‐SWCNTs within the gel matrices. Rheological experiments also demonstrated that the hybrid gel exhibited storage moduli significantly higher than those of the native gel obtained from the phenylboronic acid‐containing and diol‐containing polymers. The hybrid gel can be switched into their starting polymer (f‐SWCNTs) solutions by adjusting the pH of the system. Moreover, the hybrid gel revealed a self‐healing property that occurred autonomously without any outside intervention. By employing this dynamic character, it is possible to regenerate the used gel, and thus, it has the potential to perform in a range of dynamic or bioresponsive applications Copyright © 2013 John Wiley & Sons, Ltd.     

酞菁高分子修饰及其光电性质研究进展

酞菁拥有高度离域的二维18π电子共轭体系、易于调变的分子结构、优良的热和化学稳定性和易于处理加工等特点,可以在很宽的范围内剪裁它们的物理、光电和化学参数,其潜在的巨大应用价值已受到科学与企业界的广泛关注和研究。与[60]富勒烯一样,酞菁分子也可以通过共价键合的方式引入到高分子主链或侧链形成不同类型的高分子,亦可得到诸如酞菁网状高分子和树枝状酞菁大分子等高分子材料;与适宜的高分子材料掺杂或共混能形成含酞菁的高分子复合材料。本文详细地介绍了近年来酞菁高分子修饰与光电性质研究进展。     

Investigation of cross-resistance to a range of photosensitizers, hyperthermia and UV light in two radiation-induced fibrosarcoma cell strains resistant to photodynamic therapy in vitro

Two distinct photodynamic therapy-resistant variants of the murine radiation-induced fibrosarcoma (RIF) cell line have been isolated. One strain displayed relative resistance over the parental RIF-1 strain to treatment with the porphyrin-based compound, polyhaematoporphyrin (PHP), whereas the other strain displayed relative resistance over the RIF-1 strain to treatment using the cationic zinc (II) pyridinium-substituted phthalocyanine (PPC). The PHP-resistant strain did not display cross-resistance to PPC-mediated treatment, and vice versa. In both PDT-resistant strains, the increased resistance could not be attributed to altered cellular growth rate, antioxidant capacity or intracellular sensitizer localization. The PHP-resistant strain displayed resistance to treatment with both short (1 h) and extended (16 h) sensitizer incubation periods, which may indicate that in this strain, the resistance has arisen through an alteration in a membrane component. Conversely, the PPC-resistant strain only displayed increased resistance over the parental cells to treatment involving the short drug incubation, which is likely to reflect the existence of a threshold effect caused by the alteration of an individual cellular target. Each resistant strain has been compared to the parental strain in terms of cellular sensitivity to treatment with a range of other photosensitizers, hyperthermia, UV light and the anticancer agent cis-diamminedichloroplatinum. The PHP-resistant strain exhibited crossresistance to photosensitization treatment using exogenously added protoporphyrin IX, and also to treatment with the anionic phthalocyanine sensitizers, zinc (II) tetrasulfonated phthalocyanine and zinc (II) tetraglycine-substituted phthalocyanine. The PPC-resistant strain did not display cross-resistance to any of the treatment strategies employed in this investigation. The results of this investigation indicate that there are at least two distinct mechanisms of PDT resistance in RIF cells, and that the mechanism of PHP resistance may, to some extent depend, upon the physical nature of the sensitizer molecule.     

Formation of heterocaryotic and homonuclear bridged–dimeric complexes on surface

The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris(10-carboxydecyloxy)benzene(TCDB) template through scanning tunneling microscopy(STM). STM images of molecular adlayers of zinc tetraphenylporphyrin(Zn TPP), zinc phthalocyanine(Zn Pc), and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1:1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.     

Synthesis,characterization, and degradation of silicon(IV) phthalocyanines conjugated axially with poly(sebacic anhydride)

A novel silicon(IV) phthalocyanine with two axial poly(sebacic anhydride) chains has been synthesized by melt condensation of silicon phthalocyanine dihydroxide and oligo(sebacic anhydride). The polymer has been spectroscopically characterized and its molecular weights have been determined by gel permeation chromatography (GPC) and ¹H NMR spectroscopy. Nanoparticles with an intensity‐average apparent hydrodynamic radius of 65 ± 1 nm have been prepared from this polymer via a microphase inversion method with sodium dodecyl sulfate as the surfactant. The spherical nanoparticles contain loosely aggregated polymer chains, trapping about 90% of the water. On treatment with NaOH, these nanoparticles undergo degradation that has been monitored by laser light scattering and fluorescence spectroscopy. Because of the axial substitution, the change in the aggregation state of the phthalocyanine core of this polymer during nanoparticle formation and degradation is relatively small compared with that of the zinc(II) phthalocyanine analogue reported earlier, in which poly(sebacic anhydride) chains are linked to the periphery of the phthalocyanine ring. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 837–843, 2005     

Weak epitaxy growth and phase behavior of planar phthalocyanines on p-sexiphenyl monolayer film

We systematically investigated the weak epitaxy growth (WEG) behavior of a series of planar phthalocyanine compounds (MPc), i.e., metal-free phthalocyanine (H2Pc), nickel phthalocyanine (NiPc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), grown on a p-sexiphenyl ( p-6P) monolayer film by selected area electron diffraction (SAED) and atomic force microscopy (AFM). Two types of epitaxial relations, named as incommensurate epitaxy and commensurate epitaxy, were identified between phthalocyanine compounds and the substrate of the p-6P film. The tiny variation of the lattice constant of phthalocyanine compounds can result in different crystal orientations. The change rule of incommensurate and commensurate epitaxy was extracted. The tendency of commensurate epitaxy becomes weaker as the lattice constant b increases, while it gets stronger as the substrate temperature is elevated. Large size and continuous H2Pc films can be obtained by controlling the growth conditions. The WEG method is generally applicable in the whole family of planar phthalocyanine compounds and may be used to fabricate other high-quality organic films.     

From the conformation of a single molecule to physical networks in highly interacting polymers: A small-angle neutron study

Small-angle neutron scattering has been used to study the conformation and structure of highly interacting macromolecules in complex fluids. The evolution of the structure has been investigated from the conformation of a single molecule through an association process to the formation of physical networks. Two highly interacting polymers, an ionic polymer (consisting of a perfluorinated backbone and an ionizable hydrophilic side chain dissolved in water/alcohol mixtures) and rodlike, highly conjugated phenylene ethylene molecules (dissolved in toluene), have been studied. Highly interacting polymers often form relatively long lasting physical networks with increasing polymer concentration. The driving force, however, is system-specific, and so are the micellar systems and physical networks formed. Although the two families of polymers under consideration are entirely different chemically, their strong interaction, either ionic or through π–π coupling, results in similarities in the complex fluids formed when they are dissolved in solutions. These include elongated configurations in dilute solutions, association into micelles, and eventually coalescence into physical networks. The ionic polymers form durable stable networks, whereas the rodlike polymers form a fragile, gel-like phase. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3165–3178, 2004     

Colouring Agents for SBR Vulcanizates and Their Effects on Ageing and UV Radiation Resistance

Summary: Metal free and some metal-perylene polymers as well as some metal phthalocyanine polymers were incorporated into styrene butadiene rubber (SBR) compounds as colouring agents. The ageing and UV resistance of the vulcanizates obtained were studied in terms of their mechanical properties. The results obtained revealed that cobalt perylene and cobalt phthalocyanine polymers showed superior performance in SBR vulcanizates against thermal ageing and UV radiation. The optimum concentration of cobalt phthalocyanine polymer was found to be 1 phr (parts per hundred parts of rubber).     

Molecular Design Rule of Phthalocyanine Dyes for Highly Efficient Near‐IR Performance in Dye‐Sensitized Solar Cells

A series of zinc–phthalocyanine sensitizers ( PcS16 – 18 ) with different adsorption sites have been designed and synthesized in order to investigate the dependence of adsorption‐site structures on the solar‐cell performances in zinc–phthalocyanine based dye‐sensitized solar cells. The change of adsorption site affected the electron injection efficiency from the photoexcited dye into the nanocrystalline TiO₂ semiconductor, as monitored by picosecond time‐resolved fluorescence spectroscopy. The zinc–phthalocyanine sensitizer PcS18 , possessing one carboxylic acid directly attached to the ZnPc ring and six 2,6‐diisopropylphenoxy units, showed a record power conversion efficiency value of 5.9 % when used as a light‐harvesting dye on a TiO₂ electrode under one simulated solar condition.     

Hybrid organic/inorganic films of conducting polymers modified with phthalocyanines. II. EIS studies and film characterization

Conducting polymers were modified with Cu-phthalocyanine or Co-phthalocyanine embedded in a sol–gel matrix. The resulting films were characterized using electrochemical impedance spectroscopy, Fourier transform infrared spectroscopy and scanning electron microscopy. Electrochemical impedance spectroscopy data showed that the application of the sol–gel layer to the conductive polymer caused a noticeable increase in the impedance of the film across the frequency ranges studied. The hydrophobic character of the film was greatly influenced by the sol–gel and caused an increase in its capacitance. A modified ‘Randles’ equivalent cell was used to correlate the electrochemical parameters of the films. Elemental analysis and infrared data confirmed the presence of the phthalocyanine moieties in the film and the empirical formula of the film was estimated. The surface morphology of the sol–gel-modified conducting polymer was distinctly amorphous compared to the poly(3-methyl thiophene).     

Encapsulation of dye molecules and nanoparticles in hollow organogel fibers of a nonchiral polyurethane model compound

We present the case of a nonchiral organogelator that forms hollow fibers and encapsulates silver nanoparticles (SNP) and a dye molecule. The biscarbamate molecule (a model compound for polyurethanes), which has two hydrogen-bonding motifs symmetrically attached to n-dodecyl side chains (C(12)), gels benzonitrile with hollow fibrillar morphology. The C(12) molecules form sheets that eventually wrap into hollow fibers to form the gel network. Herein, two-component gels were prepared with C(12) as one component and SNP, phthalocyanine (Pc), or perylene (Pe) as the other. Microscopic analysis and partial melting experiments confirmed the inclusion of the silver nanoparticles and phthalocyanine into the hollow fibers. On the other hand, Pe molecules tend to form crystals at the outer surface of the C(12) fibers, which results in a significant increase in the width of the gel fibers. This difference in the behavior of Pc and Pe molecules were accounted for by their crystal geometry and significantly different crystal growth rate compared with that of C(12) fiber formation in the gels. Pc crystallizes in a needle shape that facilitates occlusion in the gel fibers, whereas Pe forms large platelets. X-ray diffraction and spectroscopic analysis of the two-component gels along with their neat components confirmed that there was no change in the packing behavior of the Pc and Pe molecules in the gels. Therefore, these are examples of two-component physical gels in which the Pc crystals are occluded within the hollow fibers of C(12) by physical mixing of the components without the aid of any inter-molecular interactions between the different components. We have thus shown that lumen-loaded gel fibers with nanoparticles and dye molecules can be prepared by the two-component gel route, provided that the above growth rate, shape, and size conditions are satisfied.     

How to Polymerize Ethylene in a Highly Controlled Fashion?

Very fast, reversible, polyethylene (PE) chain transfer or complex-catalysed "Aufbaureaktion" describes a "living" chain-growing process on a main-group metal or zinc atom; this process is catalysed by an organo-transition-metal or lanthanide complex. PE chains are transferred very fast between the two metal sites and chain growth takes place through ethylene insertion into the transition-metal- or lanthanide-carbon bond-coordinative chain-transfer polymerisation (CCTP). The transferred chains "rest" at the main-group or zinc centre, at which chain-termination processes like beta-H transfer/elimination are of low significance. Such protocols can be used to synthesise very narrowly distributed PE materials (M(w)/M(n)<1.1 up to a molecular weight of about 4000 g mol(-1)) with differently functionalised end groups. Higher molecular-weight polymers can be obtained with a slightly increased M(w)/M(n), since diffusion control and precipitation of the polymers influences the chain-transfer process. Recently, a few transition-metal- or lanthanide-based catalyst systems that catalyse such a highly reversible chain-growing process have been described. They are summarised and compared within this contribution.     

A comparative study of the cellular uptake and photodynamic efficacy of three novel zinc phthalocyanines of differing charge

Three novel substituted zinc (II) phthalocyanines (one anionic, one cationic and one neutral) were compared to two clinically used photosensitizers, 5,10,15,20-tetra(m-hydroxyphenyl)chlorin (m-THPC) and polyhematoporphyrin (PHP), as potential agents for photodynamic therapy (PDT). Using the RIF-1 cell line, photodynamic efficacy was shown to be related to cellular uptake. The cationic phthalocyanine (PPC, pyridinium zinc [II] phthalocyanine) had improved activity over the other two phthalocyanines and slightly improved activity over PHP and m-THPC. The initial subcellular localization of each photosensitizer was dependent upon the hydrophobicity and plasma protein binding. The phthalocyanines had a punctate distribution indicative of lysosomes, whereas m-THPC and PHP had a more diffuse cytoplasmic localization. A relocalization of phthalocyanine fluorescence was observed in some cases following low-level light exposure, and this was charge dependent. The anionic phthalocyanine (TGly, tetraglycine zinc [II] phthalocyanine) relocalized to the nuclear area, the localization of the hydrophobic phthalocyanine (TDOPc, tetradioctylamine zinc [II] phthalocyanine) was unchanged, whereas the distribution of the cationic phthalocyanine (PPC) became more cytoplasmic. This suggests that relocalization following low-level irradiation is a critical factor governing efficacy, and a diffuse cytoplasmic distribution may be a determinant of good photodynamic activity.     

Energy transfer from C-phycocyanin to phthalocyanine metal complex in reverse micelles

A new mimic system of photosynthetic apparatus was constructed from C-phycocyanin and phthalocyanine zinc. C-PC was solubilized in the reverse micelles of non ionic surfactant Tween-80, cosurfactant pentanol, and solvent cyclohexane, in which the overall concentration of surfactant was 20% (w/v) and the mass ratio of Tween-80 to pentanol was 4:1. When the molar ratio of water to Tween-80 (R_w)≥9.0, the characteristic properties of C-PC were maintained. When it was excited, the energy transfer from C-PC to phthalocyanine zinc took place. The energy transfer efficiency was only related with the concentration of phthalocyanine, but not that of C-PC. Furthermore, the energy transfer was roughly in keeping with Perrin formulation, which indicated that the energy transfer took place approximately through dipole-dipole interaction in rigid system. The radii of the quenching sphere were calculated from the experimental results. For example, when the concentration of phthalocyanine zinc was 2.10 × 10~(-4) mol/