Poly -phthalocyanin complex

A poly(propylenamine) dendrimer (11, Fig. 6.37) functionalised with poly-(N-isopropylacrylamide) (PIPAAm) (see Section 4.1.2) was used as dendritic host for anionic cobalt(II)-phthalocyanine complexes (a, b) as guests, which are held together by supramolecular (electrostatic and hydrophobic) interactions [57]. These dendritic complexes were investigated as catalysts in the above-mentioned oxidation of thiols, where they show a remarkable temperature dependence the reaction rate suddenly increases above 34°C. One attempted explanation assumes that the dendritic arms undergo phase separation and contraction above the Lower Critical Solubility Temperature (LCST). At this temperature the phthalocyanine complex site is more readily accessible for substrates and the reaction rate is therefore higher. 

Phthalocyanine complexes, deposited as a film on a metal of the same kind as their central metal ion, appeared to be active for hydrazine decomposition 48)-Wholly organic polymers, prepared by the dechlorination of poly vinylidene chloride 62> were also shown to be active, but the ammonia and hydrogen produced reacted with the catalyst, a problem also encountered with the polychelate catalysts. 

Some poly(oxyethylene)-substituted lutetium phthalocyanine complexes ((9) Ln = Lu, R = 0(CH2CH20) CH3, n=l-4) were prepared, but only one compound was mesomorphic ( = 3), exhibiting a Cok phase between 53 °C and 58 The analogous compounds with... 

The poly(oxyethylene)-substituted lutetium phthalocyanine complex [(CH3(0CH2CH2)30)8Pc]2Lu exhibits a tetragonal colunmar phase (Col,) between 53 and 57.6 C (a = 26.7 A Toupance et al., 1996). The high-temperature XRD pattern consists of a series of Bragg reflections which correspond to reciprocal distances in the ratio 1 V2 V4 V8. Around 4.2 A, a halo due to the molten poly(oxyethylene) chains is observed both in the mesophase and in the isotropic liquid. The melting enthalpy is 1.6 J g and the clearing... 

Amperometric detection has also been used in a flow injection method for the determination of PG, OG, and BHA using a poly(vinyl chloride) graphite composite electrode [60]. Although the detection limits obtained are relatively high (>0.2 mg/L), the method is characterized for its simplicity and low cost of instrumentation. The applicability of the method was checked by determining the analytes in soup and oil samples. A polypyrrole electrode modified with a tetrasulfonated Ni(II) phthalocyanine complex has been described as an amperometric detector in a flow injection system for the determination of PG, BHA, and TBHQ, which had been previously separated using LC [61]. The detection limit obtained for PG was 0.19 J,g/mL. 

The cobalt(II)15 and zinc(II)16 complexes of phthalocyanine(Pc), octcyano-Pc, and tetrasulfon-ato-Pc incorporated in poly(4-vinylpyridine-co-styrene) or Nafion films coated on graphite have also been examined as catalytic devices for dihydrogen electrogeneration in phosphate buffer. These catalytic systems were strongly suggested to be dominated by the electron transfer within the polymer matrix. The best catalytic film is that constituted of the nonsubstituted Con-Pc complex in poly(4-vinylpyridine-co-styrene), giving a turnover number of 2 x 10s h-1 at an applied potential of —0.90 V vs. Ag Ag Cl. 

Gold (continued) pentafluoride, structure, 27 103 peroxides, 6 343-344 phthalocyanine, preparation of, 7 64 polyhalogen complex of, 3 153 poly(pyrazolyl)borato alkyl derivatives, 42 320-321... 

Scheme 6 represents coordinate polymers. A low-molecular-weight compound with multidentate groups on both ends of the molecule grows into a linear polymer with metal ions, and the polymer chain is composed of coordinate bonds. The parquetlike polymer complexes, poly(metal-phthalocyanine) and poly(metal-tetracyano-ethylene), are classified into Scheme 7. They are formed by inserting metal ions into planar-network polymers or by causing a low-molecular-weight ligand derivative to react with a metal salt and a condensation reagent.

Water-soluble polymer-bound porphorins have been prepared by the reaction of poly(methacrylic acid) and poly(N-vinyl pyrrolidone-co-methacrylic acid) with the low-molecular weight substituted Zn complexes tetraphenylpor-phorin, phthalocyanins and naphthocyanins [67, 68]. These reactions are... 

Many other types of polymer have been prepared which exhibit semiconductivity. All obey the equation a = a0exp — E/kT. These include xanthene polymers (109, 110), polymerized phthalocyanines (111, 112), epoxides and polydiketones (86, 113), polypentadienes (114), polydicyanoacetylenes (115), polyvinylferrocene and substituted ferrocene (116, 117, 118, 119), polymeric complexes of tetracyanoethylene and metals (120), poly(vinyl chloride) and poly(vinylidene chloride) (121), polyvinylene and polyphenylene (122) and poly(Schiff s bases) (123, 124). 

Cobalt complexes find various applications as additives for polymers. Thus cobalt phthalocyanine acts as a smoke retardant for styrene polymers,31 and the same effect in poly(vinyl chloride) is achieved with Co(acac)2, Co(acac)3, Co203 and CoC03.5 Co(acac)2 in presence of triphenyl phosphite or tri(4-methyl-6- f-butylphenyl) phosphite has been found to act as an antioxidant for polyenes.29 Both cobalt acetate and cobalt naphthenate stabilize polyesters against degradation,73 and the cobalt complex of the benzoic acid derivative (12) (see Section 66.4) acts as an antioxidant for butadiene polymers.46 Stabilization of poly(vinyl chloride)-polybutadiene rubber blends against UV light is provided by cobalt dicyclohexyldithiophosphinate (19).74 Here again, the precise structure does not appear to be known. 

Copper phthalocyanine is more effective as a smoke retardant for polystyrene than most such complexes of the first row transition metals.31 Other copper compounds which are effective smoke retardants for poly(vinyl chloride) are Cu20, CuO, Cul and CuS04.5,101... 

Molecular complexes, such as the complex formed between poly(N-vinylcaibazole) and 2,4,7-trinitro-9-fluorenone, and dye-polymer aggregates were widely used as generation materials in many early applications. Since these materials are not infrared sensitive, there has been increasing emphasis on pigments. The more widely studied are various azo, phthalocyanine, squaraine, and peiylene diimide derivatives. A common feature of all of these materials is that they are polymorphic and exist in many different crystal forms. The properties are thus very sensitive to the conditions used in their preparation. Further, the sensitivity of these materials is strongly field dependent as well as dependent on the transport material. For a review of generation materials, see Law (1993). 

Halogen oxidation of planar complexes, particularly of the nickel triads that contain bidentate glyoximes or macrocyclic ligands, such as, phthalocyanines, substituted porphyrins, or tetraazaannulenes, leads to highly conducting substances that may possess chains of metal atoms as well as chains of poly halides E... 

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