Phthalocyanines metallation

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.). 

Samsonova and Nikiforov, 1984), and porphyrin and phthalocyanine metal complexes (Becker et al., 1985a, 1986b Becker and Grossmann, 1990) were tested. That a series of relatively simple anions such as the oxalate monoanion, tetraphenyl bor-anate (Ph4B ), bromide, chloride, and even tetrafluoroborate can act as donors is, at least for the last mentioned anion, surprising, but Becker et al. (1985 b) were able to trap aryl radicals and in some cases also donor radicals (Cl, COO ) by spin trapping with nitrosodurene and phenyl-tert-butylnitrone. The photochemical effect is postulated to be due to ion pairs ArNJ X-. 

High stability metallo-organic compounds such as porphyrin, phthalocyanine, metallized... 

Some coordination compounds have been used as dyes and pigments, but it must be admitted that these applications developed without reference to the fact that the compounds are complexes. Examples of paint pigments are Prussian blue and the phthalocyanines metallized azo dyes are common in the textile industry. 

Metal-dye complexes play a very important role in dyestuff technology and find applications in many other fields, e.g. in analytical chemistry.119-123 Except for copper phthalocyanine, metal-azo compound complexes are the most important and the most widely used as dyes and pigments. Typical precursors are shown in Scheme 1. 

Fig. 8. Electronic spectrum of bacteriochlorophyll a (—) extracted from antenna complexes of purple bacteria compared to the spectrum of a synthetic phthalocyanine metal complex (—). Reproduced with permission from Ref (5). Copyright Wiley-VCH.

Figure 1.28 Selected examples of dipolar phthalocyanine metal complexes...

Figure 1.29 Dipolar phthalocyanine metal complexes with large (3 values...

Metal-phthalocyanine Metal-triazolehemiporphyrazine Metal-tetraazaporphyrin... 

Metal-phthalocyanine Metal-naphthalocyanine Metal-2,3-naphthalocyanine... 

Phthalocyanine metal complexes may be prepared by various methods, the more general methods 10, 11, 34, 40, 86, 112) being illustrated in the following equations ... 

Various metal complexes such as metal phthalocyanines, metal salenes or Ru pyridyl complexes have been incorporated in molecular sieves such as cavity-structured zeolites (faujasites, supercages with 1.3-nm diameter), channel-structured aluminium phosphates (AIPO4-5, channel diameter 0.73 nm) and channel-structured silicates MCM-41 (channel diameter 3.2 nm) [51-53]. Different strategies were applied for the inclusion of the phthalocyanines. For example, whereas the zeolite-encaged phthalocyanines (1 R = -FI M = Co(II), Ru(II), etc.) are synthesized by the reaction of a transition metal ion-exchanged zeolite with phthalonitrile in a closed-bomb vessel [54], in the cases of AIPO4-5 and MCM-41 substituted derivatives of phthalocyanines were added to the mixture during the hydrothermal synthesis of the molecular sieve [55,56]. 

Phthalocyanine metal complexes in catalysis 13CRV8152. Phthalocyanines and related compounds with chalcogen functional groups 13H(87)245. 

In suptamolecular systems, in some cases (systems formed by addition of PVP, PEG, PDDA, SDS), partial or complete neutralization of the negative charge of the anionic form of the original bis-phthalocyanine is observed. In the case of micellar system CTABr lanthanide bis-phthalocyanines exist predominantly in the anionic form. The dependence of the optical density bis-phthalocyanine on their concentration in the composition of multicomponent systems revealed that in cases of different metal ions bis-phthalocyanine metal complex may be present in both molecular and associated forms. 

Phthalocyanine metal complexes in the multicomponent systems can be in three states [5] in the form of a monomer with narrow absorption band in the 665-675 nm [11-14], H-aggregates with their absorption band shifted relative to the monomer hypsochromically to -630 nm, and J-aggregates with an absorption band batho-chromically shifted relative to the monomer to wavelengths of 730-850 nm. H- and... 

Traditional template synthesis of metal phthalocyanines requires high temperatures to be used. In contrast, electrochemical template methods allow the highly efficient assembly of phthalocyanine-metal complexes in organic solvents under ambient conditions. 

Various metal complexes such as metal-phthalocyanines, metal-salenes or Ru-pyridyl complexes were incorporated in molecular sieves such as cavity-structured zeolites (faujasites, supercages with 1.3 nm diameter), channel-structured aluminum phosphates... 

Gao L, Qian X (2002) Synthesis tmd photosensitizing properties of fluoroalcoxyl phthalocyanine metal complexes. J Fluor Chem 113 161-165... 

Sorokin AB (2013) Phthalocyanine metal complexes in catalysis. Chem Rev 113 8152-8191... 

Keywords Spectroelectrochemistry Spectroelectrochemistry of phthalocyanines Phthalocyanines Metal-free phthalocyanines Metallophthalocyanines (MPcs-RlAM) bearing redox Inactive metal centers Metallophthalocyanines (MPcs-RAM) bearing redox active metal centers Electrochemistry and spectroelectrochemistry of CoPcs Electrochemistry and spectroelectrochemistry of X-Mn(lll)Pcs Electrochemistry and spectroelectrochemistry of EePcs Electrochemistry and spectroelectrochemistry of TiOPcs Sandwich metallophthalocyanines (MPc2)... 

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