Conducting Stacked Metallophthalocyanines and Related Compounds

Synthetic pathways to water-soluble phthalocyanines and close analogs

Coordination chemistry of chelating resins and ion exchangers

Cobalt phthalocyanine and iron porphyrin network polymers of intrinsic microporosity (network-PIMs) were prepared and their performance as heterogeneous catalysts compared with that of low molar mass analogues. Spiro-linked Co phthalocyanine network-PIMs prepared from preformed chlorinated phthalocyanines showed lower surface areas and lower catalytic activity than those prepared by a phthalocyanine-forming reaction from a rigid precursor incorporating a spiro-centre. However, all the phthalocyanine network-PIMs were much more effective catalysts than low molar mass Co phthalocyanine for the decomposition of hydrogen peroxide, the oxidation of cyclohexene and the oxidation of hydroquinone. An Fe porphyrin network-PIM showed a higher surface area than any of the phthalocyanine polymers and showed higher activity for the oxidation of hydroquinone, also outperforming a low molar mass FeCl porphyrin.

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Catalysis by microporous phthalocyanine and porphyrin network polymers

The optical and electronic properties of the phthalocyanine (Pc)
macrocycle make it suitable for a wide range of applications. The enormous
diversity of Pc-containing polymers, developed over thirty years of research,
offers the prospect of readily processed materials in which covalent linkages
can be used to control the ordering and arrangement of the Pc units. This
article reviews both the synthesis and study of Pc-containing polymers.
The types of polymer are classified by the way in which the macrocycle is
incorporated within the macromolecular structure as either network, main-chain
or side-chain polymers. In addition, recent work on the incorporation
of the Pc macrocycle as polymer end-groups or as the core unit in a number
of dendrimers is also described.

Phthalocyanine-containing polymers

Metal-4,4′,4″,4″′-tetracarboxyphthalocyanine [Metal = Fe(III), Co(II), Mt-taPc] were synthesized by the hydrolysis of metal-4,4′,4″,4″′-tetracarboxamidephthalocyanine (Mt-tamPc). These metal-taPc are soluble in water and in aprotic polar solvents such as N,N′-dimethylformamide. Poly(styrene) bonded Mt-taPc was synthesized by Friedel-Crafts reaction of poly(styrene) with Mt-taPc tetraacid chloride. The polymers contain about 4 mole-% Mt-Pc rings which are covalently bonded to poly(styrene). The decomposition reaction of hydrogen peroxide by catalysis with polystyrene containing Mt-Pc rings was carried out in heterogeneous aqueous media at pH 7,0. The polymer catalysts show a catalase-like activity. The activation energies with the polymer bonded Mt-Pc were found to be about half of those with Mt-taPc. From continuous flow experiments in a column, the polymer attached catalyst was found to be very stable, compared with free Mt-taPc.

Functional metal‐porphyrazine derivatives and their polymers, 4. Synthesis of poly(styrene) bonded Fe(III)‐ as well as Co(II)‐4,4′,4″,4″′‐tetracarboxyphthalocyanine and their catalase‐like activity

The decomposition reaction of hydrogen peroxide was carried out by using Fe(III)-3,4,3′,4′,3″,4″,3″′,4″′-octacarboxyphthalocyanine (Fe(III)-oaPc) as a catalyst, which has previously been reported by Boston et al. Fe(III)-oaPc is a remarkably effective catalyst for the reaction, compared with hemin, other metal-phthalocyanine compounds, or other iron complexes such as [Fe(III)-(bipy)3]X3. The kinetics of this reaction was also investigated in the pH range 5,5 – 10,5 by measuring the initial velocity, V0, of the increasing concentration of O2 using a Warburg respirometer. The reaction proceeds according the catalase-like mechanism. On the basis of the results of Sigel et al., the reaction mechanism is discussed.

Functional metal‐porphyrazine derivatives and their polymers, 3. Catalytic activity of Fe(III)‐3,4,3′,4′,3″,4″,3″′,4″′‐octacarboxyphthalocyanine for decomposition of hydrogen peroxide

A novel class of polyimides (14) containing Mt(II)-phthalocyanine rings has been synthesized by the solution condensation in N-methyl-2-pyrrolidone (NMP) of Mt(II)-[2,9or10(or2, 16or17)bis(3,4-dicarboxybenzoyl)]phthalocyanine dianhydride (Mt(II)-dahPc; Mt(II)=Co(II), Ni(II) and Cu(II); (2–4)) with aromatic diamines such as 4,4′-methylenebis(aniline), followed by thermal imidization in vacuo at 200°C. The polyamides obtained were soluble in NMP and hexamethylphosphoric triamide, having inherent viscosities up to 0,7 dl·g−1. The polyimides were stable up to 350°C, and showed room temperature-dc-resistivities in the range of 1011 to 106 Ω·cm.

Functional metal‐porphyrazine derivatives and their polymers, 2. Synthesis and properties of polyimides containing metal‐phthalocyanines

Synthesis and catalaselike activity of polystyrene‐bonded Fe(III)‐phthalocyanine

A novel class of polyimides (6a – c) containing Mt(II)-phthalocyanine rings was synthesized by solution condensation in N-methyl-2-pyrrolidone of Mt(II)-[2,9, or 10(or 2,16, or 17)bis(3,4-dicarboxybenzoyl)]phthalocyanine dianhydride [Mt(II)-dahPc: Mt(II) = Co(II), Ni(II), and Cu(II)] with 2,6-diaminopyridine, followed by thermal imidation. The polyimides showed room temperature dc-conductivities in the range of 10−12 − 10−9 Ω−1 · cm−1, and, after quaternization of the pyridine group, the conductivities increased by 1 to 3 orders of magnitude.

Functional metal‐porphyrazine derivatives and their polymers, 12. Synthesis and properties of polyimides containing a metalphthalocyanine ring and a pyridyl group

Kesayoshi Kobayashi

Papers

Functional metal‐porphyrazine derivatives and their polymers, 4. Synthesis of poly(styrene) bonded Fe(III)‐ as well as Co(II)‐4,4′,4″,4″′‐tetracarboxyphthalocyanine and their catalase‐like activity

Functional metal‐porphyrazine derivatives and their polymers, 3. Catalytic activity of Fe(III)‐3,4,3′,4′,3″,4″,3″′,4″′‐octacarboxyphthalocyanine for decomposition of hydrogen peroxide

Functional metal‐porphyrazine derivatives and their polymers, 2. Synthesis and properties of polyimides containing metal‐phthalocyanines

Synthesis and catalaselike activity of polystyrene‐bonded Fe(III)‐phthalocyanine

Functional metal‐porphyrazine derivatives and their polymers, 12. Synthesis and properties of polyimides containing a metalphthalocyanine ring and a pyridyl group