Polymers, phthalocyanine-based

Phthalocyanine-based molecular metals and conductive polymers have been prepared and investigated by 13C solid state NMR. Among others, Ge serves as a central atom219,220. However, no discussion of a special role of the metal is presented in this work. 

Fig. 2 Molecular structures of some polymers used as insulator layer in the reported phthalocyanine-based OFET devices...

Scheme 4.1 Synthesis of phthalocyanine-based sheet polymer 2.

Voltammetric sensors based on chemically modified electrodes (conducting polymers, phthalocyanine complexes) with improved cross-selectivity were developed for the discrimination of bitter solutions [50], The performance and capability were tested by using model solutions of bitterness such as magnesium chloride, quinine, and four phenolic compounds responsible for bitterness in olive oils. The sensors gave electrochemical responses when exposed to the solutions. A multichannel taste sensor was constructed using the sensors with the best stabilities and cross-selectivities and PCA of the signals allowed distinct discrimination of the solutions. 

Phthalocyanine-based polymers with shish-kebab type n -stacked structures, 7.47, are generally prepared by two different routes. These are illustrated in Scheme 7.7, where L is typically a pyrazole, diisocyanide, or p-bipyridine, and a wide variety of metals (e.g. Fe, Ru, Os) and non-metals (e. g. Si, Ge) have been used. The... 

McKeown NB, Makhseed S, Budd PM (2002) Phthalocyanine-based nanoporous network polymers. Chem Commun 23 2780-2781... 

Kobayashi M, Niwa H, Harada Y, Horiba K, Oshima M, Ofuchi H, Terakura K, Ikeda T, Koshigoe Y, Ozaki JI, Miyata S, Ueda S, Yamashita Y, Yosikawa H, Kobayashi K (2011) Role of residual transition metal atoms in oxygen reduction reaction in cobalt phthalocyanine-based carbon cathode catalysts for polymer electrolyte fuel cell. J Power Sources 196 8346-8351... 

Phthalocyanine-based polymers, such as the shish-kebab polymers (60), are also of considerable interest and significant electrical conductivities of up to ca 0.1 S/cm have been detected for chemically or electrochemically doped materials (187,188). If flexible organic substituents are present on the periphery of the phthalocyanine ring, these materials can also be soluble (at least low molecular weight fractions). 

Phthalocyanine-based self-coordinated homodimers and polymers... 

In few cases linear chain structured polymeric metal complexes were prepared. A linear polymeric phthalocyanine 60 was obtained as film by the electrochemical polymerization of the corresponding monomer [260]. The synthesis of structural uniform ladder polymers 61 based on the hemiporphyrazine structures was achieved by a repetitive Diels-Alder reaction [261,262]. Recently, linear oligomeric porphyrines covalently connected via meso-meso-positions up to 128 units were synthesized [263]. 

These results illustrate that electrochemical techniques can be employed to synthesize a vast range of [Si(Pc)0]n-based molecular metals/conductive polymers with wide tunability in optical, magnetic, and electrical properties. Moreover, the structurally well-defined and well-ordered character of the polymer crystal structure offers the opportunity to explore structure/electro-chemical/collective properties and relationships to a depth not possible for most other conductive polymer systems. On a practical note, the present study helps to define those parameters crucial to the fabrication, from cheap, robust phthalocyanines, of efficient energy storage devices. 

Catalytic activity of the aluminum-Schiff base system is dramatically enhanced by adding a bulky Lewis acid (Table 2). Inoue et al. reported that a combination of 3 with 2c led to over 1000 times acceleration in the polymerization of PO at room temperature compared with the polymerization in the absence of 2c.The resulting polymers have narrow MWDs, molecular weights close to those estimated, assuming that every molecule of 3 forms one polymer chain. The same accelerating effect of 2c is also demonstrated in the polymerization of PO by using aluminum-phthalocyanine and aluminum-tetraazaannulene complexes, 4 and 5, which exhibit very low catalytic activities without 2c. 

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