Metallophthalocyanines group

Figure 1. Molecular structures of metallophthalocyanine (MPc) complex. MPc complexes may be substituted at the peripheral or non-peripheral positions as shown. M = metal ion, and R = substituent containing terminal functional groups such as -NH2 and -OH.

Figure 2. Carton showing the integration of a substituted metallophthalocyanine (MPc) complex onto a self-assembled single-walled carbon nanotube. The substitutent R could either be terminal hydroxyl (-OH) group forming an ester bond, or amino (-NH2) group forming an amide bond.

Group IA metallophthalocyanines are prepared directly from phthalonitrile and a metal alkoxide, and easily demetallated in weak acids [Li2(Pc)] or even in alcohols [Na2(Pc), K2(Pc)].197,199... 

Group IIIB metallophthalocyanines are synthesized by the reaction of o-cyanobenzamide and metal halide, and are obtained as Min(Pc)(OH)(OH2) by reprecipitation from cone. H2S04 and... 

Group IVB metallophthalocyanines can be prepared by phthalonitrile condensation in the presence of metal chloride (Si, Ge, Sn) or oxide (Pb).197,198... 

For main group metallophthalocyanines, the ring centred redox is the only process to occur. The separation between the first oxidation and reduction potentials corresponds to the energy difference of the HOMO and LUMO, hence to the Q(0,0) absorption band at 670 nm, and is about 1.56 V. Deviation from the mean value becomes large when the size of the metal significantly exceeds the cavity of the Pc ring. The first reduction and oxidation potentials themselves (E° vs. NHE) depend on the polarizing power of the metal ion (Zejy) and are approximated by equation (32). 

With its high surface area and the accessibility to the amino groups, chitosan aerogel appeared as a good candidate to play the double role of support for metal complexes and organic base. Silica supported metallophthalocyanine are efficient catalysts for the oxidation of aromatic compounds [139]. The immobilization of hydrosoluble metallophthalocyanines (MPcS with M = Fe or Co) on chitosan aerogels afforded new heterogeneous catalysts for the aerobic oxidation of p-isophorone [140]. 

A number of papers have appeared on the optical characteristics of dendrimer polymers. A new class of photofunctional dendrimers with porphyrin groups have been made in an aryl ether framework. Effective long-range energy transfer was found to occur through the dendrimer. New dendritic metallophthalocyanines... 

Among the metallophthalocyanines, Na2(Pc) and K.2(Pc) ar th niost acid labile and dissociated in alcohols. 1 Demetallation of Group lA and IIA metals is rapid in acidic solution as expected. Group IIB, except for Zn", divalent Group IVB, trivalent Group VB metals and Fe" and Mn" are also dissociated from Pc in cone. H2SO4. Ag(Pc) is acid labile as weU as thermally unstable. 

Monomers of the group 4 metallophthalocyanines are prepared with two hydroxy groups coordinated to the metal on the fifth and sixth sites. Condensation polymerisation produces robust, highly crystalline, and rigid rod-like polymers, in which the number of subunits in the polymer (which are connected by x-oxo bridges) typically varies from about 50 to 200. The polymers can be chemically or electrochemically doped. The conductivity... 

Fig. 7.33 Strategy for the co-facial assembly of structure-enforced group 4 metallophthalocyanine assemblies. [From Marks 1990.]...

Electrochemical Routes to Polymeric Metallophthalocyanine Electrocbromic Films. The porphyrins are a group of highly colored, naturally occurring pigments containing a tetrapsrrrole porphine nucleus (Fig. 3) with substituents at the eight )3-positions of the pyrroles, and/or the four... 

The reaction between phthalonitrile and metals (finely divided or acid etched) is usually very vigorous at 250-300°C and sufficient heat is generated to maintain the reaction temperature. These compounds are monofianctional with respect to the formation of phthalocyanine rings [42,56-58]. The cyclo-tetramer-ization of four phthalonitrile molecules into a phthalocyanine macrocycle involves a reduction reaction which requires two electrons in addition to the 16 Ti-electrons from the 8 nitrile groups to yield the 18 7r-electron aromatic system. For metallophthalocyanine the two extra electrons are provided by metal or metal salts. The use of reducing coreactants such as 1,2,3,6-tetrahydropyridine or hydroquinone is effective for the conversion of phthalonitrile to phthalocyanine. The reactions are normally carried out under pressure. Bis-... 

Figure 17.2. Polymeric metallophthalocyanines having benzene rings shared in common containing carboxyl end-groups.

Silvanesan A, John SA (2008) Amino group positions dependent morphology and coverage of electropolymerized metallophthalocyanine (M = Ni and Co) films on electrode surfaces. Electrochim Acta 53 6629-6635... 

A. A. Esenpinar et al. reported the synthesis of novel zinc and cobalt metallophthalocyanines with four 7-oxy-3-(4-pyridyl)couma-rin dye groups on the periphery/nonperiphery, which were prepared by... 

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