Porphyrin, main-chain polymer

Porphyrin-based complexes pass their redox sensitivity on to the corresponding polymers. Advanced conjugated main-chain structures with attached dendrons have been introduced [220]. Grafting of porphyrin-zinc main-chain polymers onto carbon nanotubes was reported [221]. An interesting example dealing with a nonelectrochemically switched polymer was recently given. Here, polymers with porphyrin-iron end groups could be switched between linear and cyclic polymers by a dimerization procedure (Fig. 14) [222, 223],... 

When the -C=C- unit is directly bonded to the zinc porphyrin unit (polymer of type B), the Soret and Q-bands are shifted to a longer wavelength, suggesting the formation of a highly 71-conjugated system along the main chain, due to the lack of steric hindrance around the zinc porphyrin ring. 

Scamporrino, E. and Vitalini, D., Main-Chain Porphyrin Polymers. 1. Synthesis and Characterization of Polyethers Containing Porphyrin Units and Their Metal Derivatives, Macromolecules, 25, 1625, 1992. 

E. Scamporrino, D. Vitalini, Main-chain porphyrin polymers. 

Introduction of porphyrin units into main chain of water-soluble small band gap polymer. Chem Lett 335. 

Poly[(0-porph-0-CH2)j(-co-(0-bisph-0-CH2)y] Poly[(porph-0-CH2-0) (-co-(bisph-0-CH2-0)y] Main chain porphyrin polymers various copolymer compositions up to 125 000 Co and Cu transition metal inclusion with some copolymers. [161a]... 

Poly(porph-phenylenevinylene) Main chain porphyrin polymers 68% yield metallized with Zn, Cu, or Ni NMR, FTIR and cyclic voltammetric results. [163]... 

The chlorination of [MePhSi]n leads to a reactive group that is remote with respect to the main silicon chain. It is possible to modify the resulting functional polysilane in many ways. For example, recently Sakata and his research group have utilized this approach to anchor tetraphenylporphyrin units as pendant groups on the polysilane backbone (Fig. 7.21). It was observed that in this polymer an intramolecular charge transfer occurs from the silicon main-chain to the porphyrin side-chain [66]. 

Polymers with porphyrin units in the main chain and fuUerene side groups are described as electroactive [113], as well as polymers with azo-groups in the main chain [114] and triarylamines in the side chain [115-118]. By proper functionalization and architecture, even poly(thiophene) [119] and oligoaniline [120-122] and derivatives [123] become soluble in different solvents. Also, electroactive polymers derived from 2,2,6,6-tetramethyl piperidinyloxyl (TEMPO) have drawn attention, especially with respect to energy storage apphcations [124—127]. 

Fullerene-containing supramolecular polymers based on DNA templating have been reported by Chu and coworkers [96]. Cationic [60]fullerene derivahves bind onto the DNA main chain through Coulombic interachons, which gives rise to the polymeric nano-array of [60]fullerene. Shinkai and coworkers have reported photocurrent generation in a supramolecular fullerene polymer [97]. A [60]fullerene/ porphyrin/DNA ternary complex is deposited on an ITO (indium tin oxide) electrode by oxidative polymerization of E DOT. The effechve photocurrent generation is observed by light excitation of the porphyrin. 

Metal-bearing or metal-free phthalocyanines and tetraazaannulenes can be partially oxidized with iodine vapor or in solution . Substituted porphyrins may be partially oxidized with iodine . Phthalocyanines have also been prepared containing a group IIIB (e.g., Al) or group IVB (e.g., Si) main group atom that is part of an Si-O or Al-F covalent polymer. The later materials do not possess a chain of metal atoms however, they are structurally similar and exhibit similar physical properties . Except for the bisglyoximato complexes, the iodine partially oxidized substances are only poorly characterized. 

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