Platinum complexes phthalocyanine

For example, in 1963 the photochemistry of magnesium phthalocyanine with coordinated uranium cations was studied in pyridine and ethanol and indicated the occurrence of PET to the uranium complex . A rapid photoinduced electron transfer (2-20 ps) followed by an ultrafast charge recombination was shown for various zinc and magnesium porphyrins linked to a platinum terpyridine acetylide complex . The results indicated the electronic interactions between the porphyrin subunit and the platinum complex, and underscored the potential of the linking para-phenylene bisacetylene bridge to mediate a rapid electron transfer over a long donor-acceptor distance. 

Fig. 23. The molecule of phthalocyanine (platinum complex) according to Robertson (o = nitrogen atom, = carbon atom).

The phthalocyanine containing polymer films were electrochemically investigated for their electrochromic reductions and reoxidations [406,411]. Under irradiation the reduction of O2 to water was studied in photoelectrochemical cells [407,409,412]. Especially Zn(II)-phthalocyanine in poly(vinylidene fluoride) shows high cathodic photocurrents. Also the electrochemical carbox dioxide and proton reduction by Co(II)-phthalocyanines in a low concentration monomolecular in a polyvinylpyridine matrix were investigated as part of a photoenergy systems [413,414]. As an active catalyst for proton reduction also a bipyridyl platinum complex in a polymer Nafion membrane was found [415]. In order to construct such a photochemical energy conversion system, the research in this field was extended for the electrocatalytic water oxidation to O2 [416-419]. The Ru-complexes cj5-[Ru(bpy)2Cl2] and especially Ru-red ([(NHsjs Ru >-Ru(NH3)4-0-Ru(NH3)5] ) are active as electrocatalysts. 

Hiratsuka et al102 used water-soluble tetrasulfonated Co and Ni phthalocyanines (M-TSP) as homogeneous catalysts for C02 reduction to formic acid at an amalgamated platinum electrode. The current-potential and capacitance-potential curves showed that the reduction potential of C02 was reduced by ca. 0.2 to 0.4 V at 1 mA/cm2 in Clark-Lubs buffer solutions in the presence of catalysts compared to catalyst-free solutions. The authors suggested that a two-step mechanism for C02 reduction in which a C02-M-TSP complex was formed at ca. —0.8 V versus SCE, the first reduction wave of M-TSP, and then the reduction of C02-M-TSP took place at ca. -1.2 V versus SCE, the second reduction wave. Recently, metal phthalocyanines deposited on carbon electrodes have been used127 for electroreduction of C02 in aqueous solutions. The catalytic activity of the catalysts depended on the central metal ions and the relative order Co2+ > Ni2+ Fe2+ = Cu2+ > Cr3+, Sn2+ was obtained. On electrolysis at a potential between -1.2 and -1.4V (versus SCE), formic acid was the product with a current efficiency of ca. 60% in solutions of pH greater than 5, while at lower pH... 

In an interesting study, phthalocyanine complexes containing four anthraquinone nuclei (5.34) were synthesised and evaluated as potential vat dyes and pigments [18]. Anthraquinone-1,2-dicarbonitrile or the corresponding dicarboxylic anhydride was reacted with a transition-metal salt, namely vanadium, chromium, iron, cobalt, nickel, copper, tin, platinum or lead (Scheme 5.6). Substituted analogues were also prepared from amino, chloro or nitro derivatives of anthraquinone-l,2-dicarboxylic anhydride. 

The macrocyclic phthalocyanine ligand will form a complex Pt(phthalocyanine).1106 The crystal structure shows two polymorphs present because of molecular packing.1107 The platinum is in a square planar coordination geometry with a mean Pt—N distance of 1.98 A. The complex can be partially oxidized with iodine to give conducting mixed valence solids.1108 Eighteen fundamental and overtone combination bands are observed in the resonance Raman spectrum of platinum phthalocyanine, and from this data the symmetry of the excited singlets are found to be Dy.. Qlv or D2.1109... 

Palladium, platinum, and silver pthalocyaninates - 5,6-Di-substituted isoindoles were condensed in the presence of Pd(acac)2 or PtCl2 to obtain soluble octa-alkoxy-substituted phthalocyaninato palladium(II) and platinum(II) complexes [121]. Tetrakis-(neopentyloxy) phthalocyaninatosilver(II) was obtained in high yield from AgN03 and the respective metal free phthalocyanine in DMF at 75 °C [122],... 

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. 

It was reported that cobalt tetraphenylporphyrin complex (CoTPP) coated on an electrode catalyzes electrocatalytic proton reduction [21], but the activity was not very high. It has been found that metal porphyrins (such as metal tetraphenylporphyrin MTPP, 5) and metal phthalocyanines (6, MPc) when incorporated into a polymer membrane coated on an electrode exhibit high activity in electrocatalytic proton reduction to produce H2 [22,23], These polymer metal complex catalysts can be much more active than a conventional platinum-based electrode (Fig. 13-7 [23], see Experiment 13-3, Section 13-5). 

Platinum group metal phthalocyanine monomers adsorbed on GCE auto-catalyze the oxidation of cysteine depending on the nature of axial ligands. Table 7.2. When DMSO or cyanide were employed as axial ligands, autocatalytic behavior was observed. Figure 7.2. These complexes also catalyzed the oxidation of methionine, hydroxylamin, and hydrazine. Ring based redox processes were implicated in the catalytic process shown by the following mechanism (Equations (7.8H7.10)) ... 

Various metals have been explored to replace Pt, including Fe, Co, Mn, and Pb. Among these metals, cobalt and iron are often used with tetramethoxy-phenylporphyrin (TMPP) or phthalocyanine (Pc) to form metal macrocyclic complexes, which demonstrate performance comparable with Pt in neutral pH conditions. FePc supported on KJB carbon (FePc-KJB) produced a power density of 634 mW m , which is higher than 593 mW m of Pt cathode and other cathodes with metal macrocyclic complexes, including CoTMPP, FeCoTMPP, Co Pc, and FeCuPc [64]. The comparison of FePc and CoTMPP with platinum-based system demonstrated the potential of transition metal-based materials for substitution of the traditional cathode materials in microbial fuel cells [65]. Cheng et al. also demonstrated that the performance of... 

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