A Polycationic Zinc-5,15-dichlorooctaethylporphyrinate-viologen Wire

Abstract

Electropolymerization of zinc-10-bipyridinium-octaethyl-porphyrinate by cyclic scanning between −0.6 and +1.6 V yields a zigzag configured polymer, which appears as swollen, vesicular bilayer on atomic force micrographs. The same procedure leads to micrometer-long wire-shaped linear polymers, if the 5,15-methine bridge carbon atoms are blocked by chlorine substituents. The wires come in two parallel strands originating from antiparallel face-to-face dimers in the solution.

Electrochemical behavior of the tetracationic porphyrins and

“…Porphyrins substituted at the b or meso position with a single positively charged substituent such as a pyridinium, bipyridinium or phosphonium group did indeed undergo reduction of the substituent at potentials close to those of the porphyrin p system [16][17][18][19][40][41][42][43][44]. In this case, the redox pattern of the substituted groups could be strongly modified by the influence of the porphyrin moiety [37][38][39].…”

“…The reactions of electrogenerated porphyrin p-cation radicals and dications with nucleophiles to yield meso or b-substitutions are now well established and have been used to attach substituents via nitrogen, phosphorous and sulfur atoms at the meso or b positions of porphyrins [11][12][13][14][15][16][17][18][19][20][21][22]. Previous works [19,23] have demonstrated that the exhaustive oxidative electrolysis of ZnOEP in the presence of pyridine or bipyridine afford tetracationic porphyrins in which the four meso protons of ZnOEP are replaced by four pyridinium or bipyridinium groups linked via their nitrogens atoms.…”

Selective anodic preparation of 1D or 2D electroactive deposits from 5,15-bis-(9H-fluoren-2-yl)-10,20-diphenyl porphyrins

“…Even so, the 2D poly(TPP) derivatives are very low bandgap polymers with bandgap values depending on the nature of the porphyrin [21]. Finally, only few groups results [22][23][24][25] showed polymerizations leading to porphyrins incorporated in a 1D wires (Scheme 1C). To our knowledge, 1D polymerization of bis(dithienylmethoxy)-bis(terthienylmethoxy)-phosphorus(V) tetraphenylporphyrins leads to polymeric wires of tetra-and hexa-thiophene in axial position of the porphyrin unit [22].…”

“…To our knowledge, 1D polymerization of bis(dithienylmethoxy)-bis(terthienylmethoxy)-phosphorus(V) tetraphenylporphyrins leads to polymeric wires of tetra-and hexa-thiophene in axial position of the porphyrin unit [22]. Giant polymer fibers were also obtained by electropolymerization of zinc-5,15-dichloro-10-[4,4 0 -bipyridinium-hexafluorophosphate]-porphyrinate [23] and more recently, the anodic oxidation of a 5,15-bis(4-(2-(3,4-ethylenedioxy)thienyl)phenyl)-10, 20-diphenylporphyrin gave a very stable and highly electroactive deposit [24]. Molecular wires of meso-meso-linked porphyrins were obtained by anodic oxidation of diarylporphyrins [25].…”

Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

“…The syntheses of the copolymers were achieved via our electropolymerization method, as reported earlier [29,31,32]. It relied on the addition of the dipyridyl-substituted Lindqvist-type polyoxovanadate [V 6 O 13 {(OCH 2 ) 3 CNHCO(4-C 5 H 4 N)} 2 ] 2-(Py-POM-Py) to an electro-generated dicationic porphyrin by iterative scans between -1.10 V and +1.60 V vs. SCE (Fig.…”