Phthalocyanine copper complex, synthesis

A large class of coordination compounds, metal chelates, is represented in relation to microwave treatment by a relatively small number of reported data, mainly p-diketonates. Thus, volatile copper) II) acetylacetonate was used for the preparation of copper thin films in Ar — H2 atmosphere at ambient temperature by microwave plasma-enhanced chemical vapor deposition (CVD) [735a]. The formed pure copper films with a resistance of 2 3 pS2 cm were deposited on Si substrates. It is noted that oxygen atoms were never detected in the deposited material since Cu — O intramolecular bonds are totally broken by microwave plasma-assisted decomposition of the copper complex. Another acetylacetonate, Zr(acac)4, was prepared from its hydrate Zr(acac)4 10H2O by microwave dehydration of the latter [726]. It is shown [704] that microwave treatment is an effective dehydration technique for various compounds and materials. Use of microwave irradiation in the synthesis of some transition metal phthalocyanines is reported in Sec. 5.1.1. Their relatives - porphyrins - were also obtained in this way [735b]. 

Most reported phthalocyanine derivatives (sulfo-, nitro-, amino-, triphenylmethyl-, polymeric, etc.) are copper complexes, although at present the synthetic chemistry of other d- and /-metal Pc derivatives is being rapidly developed (Examples 30-36) [5,6,116-118]. Some of them (in particular, copper phthalocyanine sulfonic acids) are of industrial interest because of their usefulness as dyes. Phthalocyanine sulfonic acids themselves are prepared both by urea synthesis from sulfonated phthalic anhydride and by the sulfonation of the phthalocyanine [6], Some substituted metal phthalocyanines can be obtained by chemical or electrochemical reduction [118e]. Among a number of reported peculiarities of substituted phthalocyanines, the existence of three electronic isomers for magnesium derivative PcMn was recently confirmed [118f]. 

The use of metal ions as templates for macrocycle synthesis has an obvious relevance to the understanding of how biological molecules are formed in vivo. The early synthesis of phthalocyanins from phthalonitrile in the presence of metal salts (89) has been followed by the use of Cu(II) salts as templates in the synthesis of copper complexes of etioporphyrin-I (32), tetraethoxycarbonylporphyrin (26), etioporphyrin-II (78), and coproporphyrin-II (81). Metal ions have also been used as templates in the synthesis of corrins, e.g., nickel and cobalt ions in the synthesis of tetradehydrocorrin complexes (64) and nickel ions to hold the two halves of a corrin ring system while cycliza-tion was effected (51), and other biological molecules (67, 76, 77). 

The example given here is copper phthalocyanine (13) its synthesis is illustrated in Figure 2.3, and is one of the easiest to prepare. Many metal complexes are known but the copper complex, shown in Figure 2.4, is perhaps the most representative. The initial reaction often generates the /3-form of the material which can be transformed to the more stable a-form by grinding and precipitation... 

Works.that have recently appeared regarding the use of microwave radiation for synthesis of tetraarylporphyrins, phthalocyanines and their metallocomplexes with Er and Gd in the dimethylacetamide medimn in presence of dry lithimn chloride [5, 6], induced us to cany out similar syntheses on the example of TPP [7] and 5,10,15,20-tetrakis(3-methoxyphenyl)porphyrin. This porphyrin is interesting due to fact that on the basis of its dihydroderivative Bormet [8] created a drag Foscan, which is used for the cancer photodynamic therapy. Octabromderivative FFP-Br was synthesized from the TPP copper complex [9]. 

Bacteriochlorins, 851 Barbituric acid metal complexes, 798 Barium alkoxides synthesis, 336 Barium complexes phthalocyanines, 863 porphyrins, 820 Becium homblei copper accumulation, 964 Benzaldehyde, 2-amino-self-condensation aza macrocycles from, 900 Benzamide, o-mercapto-metal complexes, 655 Benzamide oximes metal complexes, 274 Benzamidine, /V, V -diphenyl-metal complexes. 275 Benzene, 1,2-diamino-reactions with dicarbonyl compounds aza macrocycles from, 902 Benzene, 4 methylthionitroso-metal complexes, 804 Benzenedithiolates metal complexes, 605... 

The insolubilities of phthalocyanines made their analysis difficult and it took some time before a satisfactory structure was elucidated. Initial work was undertaken by the Linstead group at Imperial College in the 1930s that culminated in a series of six back to back papers published in 1934 [14], It was also Linstead who named the compounds in recognition of their synthesis from phthalic anhydride and similarity to the blue cyanine dyes. Definitive characterization of the nickel, platinum and copper phthalocyanine complexes, together with the metal-free compound, was revealed in 1935 following the publication of their X-ray structures by Robertson [15] the copper and metal-free compounds are illustrated in Fig. 7.5. 

Anionic copper(II)phthalocyanine monosulphonate (CuPcMs) and copper(II) phthalocyanine tetrasulphonate (CuPcTs) complexes have been successfully intercalated into the intergallery of Mg-Al layered double hydroxides through direct synthesis method. XRD results indicated an inclined orientation of the anion in the interlamellar space. A better thermal stability was noticed for the macrocycle ligand upon intercalation. The visible spectra showed a hyspochromic shift upon intercalation indicating disturbance of the macrocycle ligand pltmarity. An enhanced activity for the selective oxidation of cyclohexanol to cyclohexanone was observed for the intercalated complex in comparison with neat complex. 

The phthalocyanines, as copper, cobalt and nickel complexes, discovered in the 1920 s, form a versatile group of pigments they display high color-fastness with blue to green shades, depending on the degree of halogen substitution. Phthalocyanines can be produced by the widely-used synthesis from phthalic anhydride and urea as well as from phthalodinitrile. 

Thus, in examples of synthesis of tetraazamacrocyclic compounds on nickel ions (mainly) and on copper(II), square-planar system assembling is realised [38,47-49]. Guanidium ion promotes building of 27-crown-9-ether [60]. o-Aminobenzaldehyde self-condensation on the copper ion as matrix results exclusively in forming a complex with TAAB [67]. When using nickel(II) or cobalt(II) as templates under the same conditions, two types of macrocyclic azomethine systems - TAAB and TRI - may be synthesised [67-71]. Macrocychsation of phthalonitrile on the anisotropic matrix 0=U=0 ends with obtaining the so-called superphthalocyanine product [U02(L29)] [72, 73], rather than with the isolation of the corresponding complex with the phthalocyanine (Pc), as observed for other metal ions (Eq. 1.18) [11,74]. 

---