Phthalocyanine salts

The synthesis of the crystal modification is controlled primarily by the finishing technique of the crude pigment. There are basically two different methods to produce a finely dispersed pigment treatment with acid to form copper phthalocyanine salts, followed by precipitation in water on the one hand, and mechanical treatment (milling, kneading) on the other hand. The following methods are used ... 

For the tetraselenatetracene and phthalocyanine salts it appears that the electronic correlations are weak. In these molecules, larger than the TTF type, it turns out that U < 41, and the delicate balance between the kinetic and the correlation energies seems to be destroy (i.e. U 2V 41 ). Besides, one must repeat that the transverse interactions have to be included, to account for the transition temperatures (see above), even if it is often delicate to estimate these parameters. As a conclusion, we can say that this approach may give clues as to why, among so many series of molecular conductors, only a few exhibit an AF or SC ground state. 

It has a limited use in the preparation of the phthalocyanine pigments into which it is readily converted on heating with metallic salts. 

Cm ORINE OXYGEN ACIDS AND SALTS - DICm ORINE MONOXIDE, HYPOCm OROUS ACID, AND HYPOCm ORITES] (Vol 5) Perchlorobromo copper phthalocyanine [1328-53-6]... 

Phthalocyanine compounds have been synthesized with various metals (1,2,4). The most important metal phthalocyanines are derived from phthalodinitnle, phthaUc anhydride. Pc derivatives, or alkaU metal Pc salts. 

Metal phthalocyanines may also be prepared using alkaU metal salts or from metal-free phthalocyanine by boiling the latter in quinoline with metal... 

Very unstable modifications, like the reddish, chlorine-free a-copper phthalocyanine, can be stabilized with amides or salts of copper phthalocyanine sulfonic acids (59—63). Mixture with other metal phthalocyanines, eg, tin, vanadium, aluminum, or magnesium, also inhibits crystallization change and poor performance in binders and prints (flocculation) due to the hydrophobic character of unsubstituted phthalocyanines. 

Phthalocyanine Dyes. In addition to their use as pigments, the phthalocyanines have found widespread appHcation as dyestuffs, eg, direct and reactive dyes, water-soluble dyes with physical or chemical binding, solvent-soluble dyes with physical or chemical binding, a2o reactive dyes, a2o nonreactive dyes, sulfur dyes, and wet dyes. The first phthalocyanine dyes were used in the early 1930s to dye textiles like cotton (qv). The water-soluble forms Hke sodium salts of copper phthalocyanine disulfonic acid. Direct Blue 86 [1330-38-7] (Cl 74180), Direct Blue 87 [1330-39-8] (Cl 74200), Acid Blue 249 [36485-85-5] (Cl 74220), and their derivatives are used to dye natural and synthetic textiles (qv), paper, and leather (qv). The sodium salt of cobalt phthalocyanine, ie. Vat Blue 29 [1328-50-3] (Cl 74140) is mostly appHed to ceUulose fibers (qv). 

Phthalocyanine Dyes. These days are synthesized as the metal complex on the textile fiber from, eg, phthalonittile and metal salts. A print paste typicaUy contains phthalonittile dissolved in a suitable solvent and nickel or copper salts. During a heat or steam fixation of 3—5 min, the dye is formed. The color range is restricted to blue and green shades and can be influenced to some extent by the choice of metal salt. A hot acid bath during afterscouting completes the process. 

Green-yellow salts of the tetrahedral [MX4] (X = Cl, Br, I) ions can be obtained from ethanolic solutions and are well characterized. Furthermore, a whole series of adducts [MnX2L2] (X = Cl, Br, I) are known where L is an N-, P- or A -donor ligand, and both octahedral and tetrahedral stereochemistries are found. Of interest because of the possible role of manganese porphyrins in photosynthesis is [Mn (phthalocyanine)] which is square planar. The reaction of aqueous edta with MnC03 yields... 

The industrial manufacture of copper phthalocyanine began in 1935 by ICI, which developed its production from phthalic anhydride, urea and metal salts. In 1936 and 1937. the I.G. Farbenindustrie and Du Pont followed, and the most important of the phthalocyanines. PcCu, is now produced worldwide. Due to its favorable properties such as light, chemical and... 

However, they can also be prepared by metal exchange from alkali-metal phthalocyanines. If proton donors like hydrochloric acid, water or methanol are added to the reaction mixture of a freshly prepared alkali-metal phthalocyanine, metal-free phthalocyanines (PcH2) are formed (see Section 2.1.4.1,). If, on the other hand, the appropriate metal salt is added to a solution of an alkali-metal phthalocyanine, the product is the metalated compound (PcM) (see Section 2.1.6.). 

Due to its commercial importance, the synthesis of copper phthalocyanine (PcCu) is the best investigated of all the phthalocyanines. Copper phthalocyanine is prepared from phthalonitrile and copper(I) chloride without solvent137 and also in a melt of urea.229,277 Additionally, the insertion of copper into metal-free phthalocyanine in butan-l-ol and pentan-l-ol is possible. The copper salts used in this case are copper(I) chloride112 and copper(II) acetate.290 Starting from copper(II) acetate, copper phthalocyanine can also be prepared in ethylene glycol.127 As mentioned above, copper phthalocyanine often occurs as a byproduct of the Rosenmund-von Braun reaction. To increase the yield of the phthalocyanine the solvent dimethylformamide can be substituted by quinoline. Due to the higher boiling point of quinoline, the copper phthalocyanine is the main product of the reaction of copper(I) cyanide and 1,2-dibromoben-zene.130... 

Cyclization of 3,4,5,6-tetrachlorophthalic anhydride (8) in the presence of urea, Ihe appropriate metal salt and catalytic amounts of ammonium molybdate(VI) in nitrobenzene at high temperature leads to phthalocyanine 9. 

Treatment of 4-substituted phthalimides with a copper(II) salt, urea, and ammonium molyb-date(VI) yields phthalocyanines 5.407 Again, structural isomers are obtained. 

Unsubstituted phthalocyanines are accessible by the reaction of phthalonitrile with metals, alloys, metal salts or metal coordination compounds. Often a mixture of these compounds and phthalonitrile are heated without solvent beyond the melting point of phthalonitrile. 

Examples of phthalocyanines 10 formed by treating an appropriate metal salt in solution with a 4-substituted phthalonitrile 9 are given below. 

The exchange of lithium in a dililhium phthalocyanine is a useful tool to prepare metal (e.g., zinc) or metal-free phthalocyanines. For this purpose, the dilithium phthalocyanine is prepared by reaction of phthalonitrile and lithium alkoxide in an alcohol, e.g. pentan-l-ol. In most cases, the lithium phthalocyanine is not separated but directly converted into the respective phthalocyanine by treatment with metal salts or, in the case of metal-free phthalocyanine, with acid or water. 

If lanthanide salts (e.g., Yb(OAc)3 H20) are used as the metal compound, hexadecasub-stituted bis(phthalocyanines) can be prepared starting from 2,3,9,10,16.17,23,24-octa-substituted metal-free phthalocyanines.201... 

Metal atoms with a stable oxidation state of + IV are known to form unsubstituted bis(phthalo-cyanines) 9,10. They can be prepared by the reaction of a metal phthalocyanine, or an appropriate metal salt, and an alkali-metal phthalocyanine. 

Fig.1. Structures of porphyrin 1, chlorophyll 2, and phthalocyanine 3. In the presence of metal salts M"+X (M=metal, X=counter anion, n=oxidation state or number of counter anions), porphyrins produce chelate complexes. Some metal chelates of the porphyrins, such as ZnPor, form further coordination bonds with other ligands such as pyridines...

Unique combinations of properties continue to be discovered in inorganic and organometallic macromolecules and serve to continue a high level of interest with regard to potential applications. Thus, Allcock describes his collaborative work with Shriver (p. 250) that led to ionically conducting polyphosphazene/salt complexes with the highest ambient temperature ionic conductivities known for polymer/salt electrolytes. Electronic conductivity is found via the partial oxidation of unusual phthalocyanine siloxanes (Marks, p. 224) which contain six-coordinate rather than the usual four-coordinate Si. 

The first catalysts reported for the electroreduction of C02 were metallophthalocyanines (M-Pc).126 In aqueous solutions of tetraalkylammonium salts, current-potential curves at a cobalt phthalocyanine (Co-Pc)-coated graphite electrode showed a reduction current peak whose height was proportional to the C02 concentration and to the square root of the potential sweep rate at a given C02 concentration. On electrolysis, oxalic acid and glycolic acid were detected, but formic acid was not. Mn and Pd phthalocyanines were inactive, while Cu and Fe phthalocyanines were slightly active. At the potentials used for C02 reduction, M-Pc catalysts would be in their dinegative state, and the occupied dz2 orbital of the metal ion in the metallophthalocyanine was suggested to play an important role in the catalytic activity. 

Mixed condensation of 4-sulfophthalic acid with other substituted phthalic acids (typically >200 °C, metal salt, urea, ammonium molybdate catalyst Figure 6) again gives mixtures.246-248 Routes which lead predominantly to monosulfonic acids of zinc(II) phthalocyanine and related compounds have been described.247,250... 

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