Titanium phthalocyanine

Abstract This chapter discusses the electronic absorption spectra and electrochemistry of phthalocyanine complexes which are redshifted to 730nm and beyond. These are mainly manganese phthalocyanine derivatives and phthalocya-nines containing sulfur substituents. The chapter concentrates mainly on the work done during the last 10 years. There are 96 references quoted and three detailed tables on the electronic absorption spectra, redox potentials, and analytes that are electrocatalyzed using manganese and titanium phthalocyanine complexes. 

Muranaka A, Okuda M, Kobayashi N, Somers K, Ceulemans A (2004) Recognition of chiral catechols using oxo-titanium phthalocyanine. J Am Chem Soc 126(14) 4596-4604... 

Nombona N, Tau P, Sehlotho N, Nyokong T (2008) Electrochemical and electrocatalytic properties of a-substituted manganese and titanium phthalocyanines. Electrochim Acta 53(7) 3139-3148... 

Pigments and dyes Titanium dioxide, mono and disazo compounds phthalocyanines, anthraquinones... 

There are other metal complexes, such as tin, aluminum, magnesium, iron, cobalt, titanium, and vanadium complexes, which are similarly useful in stabilizing a particular phthalocyanine modification. Moreover, carboxy, carbonamido, sulfo, or phosphono-copper phthalocyanine may be admixed during fine dispersion of the pigment. 

The phthalic anhydride/urea process may also be employed to convert tetra-chloro phthalic anhydride to green copper hexadecachloro phthalocyanine by condensation. In this case, titanium or zirconium dioxides, particularly in the form of hydrated gels, are used instead of the molybdenum salts which are used in the phthalic anhydride process [23]. There is a certain disadvantage to the fact that the products lack brilliance and require additional purification. 

Copper Perbromo Phthalocyanine Green may also be obtained from tetra-bromo phthalic anhydride by the phthalic anhydride/urea process in the presence of titanium or zirconium catalysts. This route has not yet been introduced on a commercial scale. 

Addition of low levels of certain additives to PBT can be a desirable way to enhance properties. The most common additives are colorants. Both pigments and dyes can be used to color PBT. Carbon black and titanium dioxide are most widely used. Carbon black and other pigments, for example, phthalocyanines, can also act as a nucleant for speeding crystallization. 

Very few complexes have been examined. It is known that (Pc)TiCl can be converted t (Pc)TiO.152 Dichloro(phthalocyaninato)titanium(lV) can be synthesized via equation (27). Th reaction is a convenient one, inasmuch as the titanium(III) furnishes the electrons necessary t convert phthalonitrile to the phthalocyanine anion.153... 

Other industrial uses of aluminum flake include the building industry (production of aerated concrete) and the chemical industry (e.g., production of titanium dioxide, pyrotechnics, and explosives). Copper powder in flake form is used in the chemical industry (e.g., for phthalocyanine production, for lubricants). 

TV-phenylbenzohydroxamic acid, 506, phthalocyanines, 865 polypyrazolylborates, 248 porphyrins, 823 pseudohalides, 228 Titanium(III) complexes octaethylporphyrin reaction with dioxygen, 325 Titanium(IV) complexes 1,3-diketones, 376 triazines... 

Syntheses of MPc from phthalodinitrile or phthalic anhydride in the presence of urea are the two most important laboratory and industrial methods. They were also used originally by Linstead et al. [8,9], This procedure allows the production of many phthalocyanine compounds [35-37], Catalysts such as boric acid, molybdenum oxide, zirconium and titanium tetrachloride, or ammonium molybdate are used to accelerate the reaction and improve the yield [36,37], Ammonium molybdate is especially effective. Reaction is carried out either in a solvent or by heating the solid components. When metal chlorides and phthalodinitrile are used as starting materials, the reaction products are partially chlorinated (e.g.,7). 

Mbambisa G, Tau P, Antunes E, Nyokong T (2007) Synthesis and electrochemical properties of purple manganese(III) and red titanium(IV) phthalocyanine complexes octa-substituted at non-peripheral positions with pentyl thio groups. Polyhedron 26(18) 5355-5364... 

Abbreviations AD, asymmetric dihydroxylation BPY, 2,2 -bipyridine DMTACN, 1,4-dimethyl-l,4,7-triazacyclonane EBHP, ethylbenzene hydroperoxide ee, enantiomeric excess HAP, hydroxyapatite LDH, layered double hydroxide or hydrotalcite-type structure mCPBA, meta-chloroperbenzoic acid MTO, methyltrioxorhenium NMO, A-methylmorpholine-A-oxide OMS, octahedral molecular sieve Pc, phthalocyanine phen, 1,10-phenantroline PILC, pillared clay PBI, polybenzimidazole PI, polyimide Por, porphyrin PPNO, 4-phenylpyridine-A-oxide PS, polystyrene PVP, polyvinylpyridine SLPC, supported liquid-phase catalysis f-BuOOH, tertiary butylhydroperoxide TEMPO, 2,2,6,6-tetramethyl-l-piperdinyloxy TEOS, tetraethoxysilane TS-1, titanium silicalite 1 XPS, X-ray photoelectron spectroscopy. 

Yu JC, Xie Y, Tang HY, Zhang L, Chan HC, Zhao J. Visible light-assisted bactericidal effect of metal phthalocyanine-sensitized titanium dioxide films. J Photochem Photobiol A Chem 2003 156 235 11. 

The EPA continues to refine and improve theTRI reports.The first year s report, for example, required the reporting of releases of titanium dioxide as a toxic substance. In later years, phthalocyanine blue and green pigments and barium sulfate have been delisted, as data have been submitted to the EPA proving their lack of toxicity. 

Suzuki, Y, Fujita, T., Hayashi, Y. and Okayasu, H. (1989 ). Novel crystal type copper phthalocyanine blue pigment—obtained fromphthalic anhydride, urea, cuprous chloride, titanium tetrachloride and sulphophthalic acid. Sumitomo Chemical Co. Ltd. Patent JP 1153756. Chem. Abstr., Ill, 235057y. [267]... 

Recent reviews of the phthalocyanines by Lever (57) and by Moser and Thomas 66) are available. Complexes of phthalocyanine with all of the first row transition elements, excepting scandium, have been prepared. However, titanium and vanadium phthalocyanines are known only as the oxy- or chloro-compounds and are not then strictly square planar. That phthalocyanine has considerable ability to promote the square planar configuration is further demonstrated by the existence of the chromium (III) and manganese(II) complexes (57). 

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