Phthalocyanines zinc complexes

Tetrakis(2,2,3,3,4,4, 5, 5 -octafluoropentoxy) phthalocyanine zinc was synthesized and characterized demonstrating the effects of the strongly electron-withdrawing groups on the electronic and spectroscopic properties of the complex.832 Zinc phthalocyanate,... 

Dinaphthotetraazaporphyrins are structural isomers of phthalocyanines. The zinc complex was formed and the properties compared to zinc phthalocyanines demonstrating a lower fluorescence quantum yield for the zinc-fused naphthalene porphyrin (D2h symmetry) vs. the zinc phthalocyanine (D4h)S36... 

Zinc complexes of at number of bulky polydentate ligands (36) which are structurally related to phthalocyanines have been reported by Gagne.350... 

Phthalimide, JV-thio-metal complexes, 800 Phthalocyanines, 863-870 chelate complexes, 374 demetallation, 863 IR spectra, 861 mass spectra, 861 metallation, 863 NMR, 861 photochemistry, 869 reactions, 863 at metal, 869 redox chemistry, 870 spectra, 860 synthesis, 861 two-metal complexes, 868 Phytic acid zinc complexes, 985 2-Picoline... 

Mantareva V, Kussovski V, Angelov I, et al. Photodynamic activity of water-soluble phthalocyanine zinc(II) complexes against pathogenic microorganisms. Bioorgan Med Chem 2007 15 4829-35. 

The 31P NMR spectra of nickel and zinc complexes of tetrakis(ethyl-phenylphosphinate)-substituted phthalocyanines showed the presence of several constitutional isomers.398 The formation of trimetallic (Ni2Pt) complexes by the reaction of nickel me.vo-tetratolylporphyrin derivatives with PtCl2-con-taining species has been shown by H and 13C NMR spectroscopy to be diastereoselective.399 The 111 NMR spectrum of nickel(II) umecyanin (a stellacyanin with an axial Glu ligand, demonstrates the unidentate coordination of Glu via the side-chain amode oxygen atom.400... 

Figure 4.4 Structural formulae (zinc complexes) of (a) tetrasulfonated phthalocyanine (TSPc different isomers present) and (b) tetrasulfonated tetraphenylporphyrin (TSTPP).

Figure 4.5 Redox potential for the first reduction of zinc complexes of phthalocyanines dissolved in DMF and Hammett Etr values determined for a variety of differently substituted ligands. Reprinted with permission from [160].

The interplay of different dye molecules present during the electrodeposition reactions of dye-modified ZnO was studied for zinc complexes of tetrasulfonated phthalocyanine (TSPcZn, Figure 4.4a) and tetraphenylporphyrin (TSTPPZn) in which case both dyes (Figure 4.4b) were simultaneously adsorbed to form a hybrid material with ZnO [258]. The typical absorption bands for both dyes were detected. Films of TSPcZn/ZnO consisted of larger particulate domains when compared with TSTPPZn/ZnO or (TSTPPZn + TSPcZn)/ZnO. The presence of the porphyrin stabilized the phthalocyanine on the ZnO since a greater amount of TSPcZn was adsorbed. In the photosensitization of ZnO, TSPcZn and TSTPPZn worked... 

The effect of the metal ion was investigated, too (Figure 27). Except for the lead complex, all complexes showed an enantiotropic, columnar mesophase characterized as Coh by miscibility studies with the zinc complex. As for the phthalocyanines, the lead ion was located out of the porphyrin plane but here, this distortion and the consequent disturbance of the tt stacking led to total suppression of the mesophase. The transition temperatures were similar for all mesomorphic metal complexes, with a perceptible effect of the metal on the clearing temperatures, which... 

The CT by oxidation of phthalocyanine zinc(II) (Zn Pc) in a Nafion film was also studied using a potential-step chronocoulospectrometry (PSCCS) technique [34]. Absorption spectra of Zn Pc/Nafion indicated the formation of the Zn Pc dimer, and the equilibrium constant between its monomer and dimer in the Nafion film was 75 M . The plots of bulk CT rate vs. total Zn Pc concentration gave a downwardly deviating curve, and the process was analyzed considering the equilibrium between the monomer and the dimer. The analysis result showed that CT takes place by physical displacement of the Zn Pc monomer with kp = 3.3 x 10 s and not by charge hopping, and that the contribution of the dimer to the CT is neghgible. The macrocyclic complexes such as [Co TTP]" " and Zn Pc are known to be an active electrocatalyst. The obtained CTs by [Co TPP] and Zn Pc should be taken into... 

Because of space limitations, we will only briefly discuss the most basic application in the area of porphyrin optical spectra. Much work has already been done in this area, both with TDDFT and related methods. The TDDFT applications include free base porphin and its ss-octahalogenated derivatives, the porphyrinato-porphyrazinato-zirconiumhV) complex, NiP, NiPz, NiTBP, and NiPc, zinc phthalocyanine, chlorophyll a, zinc complexes of porphyrin, tetraazaporphyrin, tetrabenzoporphyrin, phthalocyanine, phenylene-linked free-base and zinc porphyrin dimers, metal bis(porphyrin) complexes a series of porphyrin-type molecules, and many more. We refer to ref. 75 for an extensive discussion of TDDFT calculations on the spectra of porphyrins and porphyrazines, as well as their interpretation. For further theoretical work on porphyrines, we mention ref. 76 and other papers in that special issue. 

Because in most cases no clear lUPAC nomenclature exists for metal-containing macromolecules or macromolecular metal complexes, it is not possible to obtain by a Chemical Abstract literature search a detailed information on them. One has to look for each individual metal, metal ion, metal complex, metal chelate, ligand or also polymer. For type I usually rational nomenclature is used (for example cobalt(II) complex with/ of poly(4-vinylpyridine) or 2,9,16,23-tetrakis(4-hydroxyphenyl)phthalocyanine zinc(II)... 

The homo- and copolymerization of porphyrins and phthalocyanines being substituted by four methacryloyloxy or 2,4-hexadienoyloxy groups, such as the zinc complexes of 2,9,16,23-tetrakis(4-(methacryloyloxy)- and 2,9,16,23-tetrakis(4-(ll-metha-cryloyloxyundecyloxy)phenoxy)phthalocyanines 50 and 51 were investigated [227]. The copolymerizations were carried out with styrene in DMF initiated by AIBN at 60 °C. In order to avoid crosslinking and to obtain DMF soluble copolymers, only a small... 

Water soluble cobalt(ll) 2,9,16,23-tetrasulfophthaloeyanine, zinc(II)-2,9,16,23-tetrasulfo-phthalocyanine, zinc(ll)tetracarboxyphthalocyanine, and non-metallic sulfophthalocyanine complexes are catalysts and photocatalysts for the oxidation of sulfide, sulfite and thiosulfate ions by dioxygen. Typical conditions are 293 K, 1 atm Oi and pH 9.24 in aqueous solutioaThe cobalt phthalocyanine complexes show high catalytic activity only in the... 

Notably, this metal-mediated concept, namely, coordination of a fullerene-pyridine ligand by a macrocyclic r-system, is very general and has been successfully extended to zinc complexes of phthalocyanines, porphycenes and corrphycene macrocycles. Interestingly, the binding strength reveals a close resemblance to the oxidation potential of the macrocyclic s -system porphycene > porphyrin. 

The recoil chemistry of Cd phthalocyanine has been studied by following the behaviour of the In daughter product. The argument is that no bond rupture occurs in the beta decay, and all observed effects are due to the (n,y) reaction during the production of Cd. This is contrary to general experience in p decay studies (see Section 7). The evidence is that cadmium phthalocyanine, which is ionic, anneals even at 20 C, in contrast to crystals of the copper and zinc complexes. A detailed analysis of the annealing kinetics is given. ... 

Once again, a representative sample of zinc phthalocyanine complexes is presented highlighting particular areas of importance. 

The X-ray structure of zinc naphthalocyanate has been determined with Zn—N bond lengths of 1.983(4) A.829 Pentanuclear complexes with a zinc phthalocyanine core and four ruthenium subunits linked via a terpyridyl ligand demonstrate interaction between the photoactive and the redox active components of the molecule. The absorbance and fluorescence spectra showed considerable variation with the ruthenium subunits in place.830 Tetra-t-butylphthalocyaninato zinc coordinated by nitroxide radicals form excited-state phthalocyanine complexes and have been studied by time-resolved electron paramagnetic resonance.831... 

The redox potentials of zinc-substituted phthalocyanines are shown to be linearly dependent on the total Hammett substituent constant.837 In 1987, Stillman and co-workers used the absorption and magnetic circular dichroism spectra of the zinc phthalocyanine and its 7r-cation-radical species to assign the observed bands on the basis of theoretical calculations. The neutral and oxidized zinc phthalocyanine complexes with cyanide, imidazole, and pyridine were used with the key factor in these studies the stability of the 7r-cation-radical species.838 The structure of zinc chloro(phthalocyaninato) has been determined and conductivity investigated.839... 

A porphyrin compound with a 2,9-dimethyl- 1,10-phenanthroline functionality fused at the beta-pyrrole positions is a phthalocyanine analog, and formed a complex with zinc in the cavity and a further zinc binding to the phenanthroline group. The absorption and emission spectra of the compound with and without the external zinc demonstrated the strong effects of the second metal binding on the porphyrin 7r-system.840... 

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