Poly Tetraphenylporphyrins

Synthesis oxidative eleetropolymerization of the respective free or metallated tetra-phenyl—or fluorenyl or spirobifluorenyl—porphyrin [722]. 

Redox reactions four redox waves in the potential region between 0.1 and 2 V vs. Fc/Fc+ in CH2CI2/TBAPF6 (p-doping) and two pairs of waves between — 1 and —2 V (n-doping). 

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SWCNTs-porphyrin nanosensors have been fabricated for monitoring toxic substances in the enviromnent [215], Free-base, Ru and Fe octaethyl-and tetraphenyl-substituted porphyrins provided good selectivity and sensitivity to various VOCs tested (acetone, butanone, methanol, ethanol). Nonco-valently functionalized SWCNTs with iron tetraphenylporphyrin were used for benzene detection [216], SWCNTs noncovalently functionalized with copper phthalocyanine and free-base porphyrins were used as sensing layers for the detection of toluene [217]. Also, MWCNTs were used as sensors for benzene, toluene, and xylene, when fnnctionalized with metal tetraphenyl porphyrins [218], SWCNTs-poly(tetraphenylporphyrin) hybrid was prepared and tested as a low-power chemiresistor sensor for acetone vapor [219]. A chemiresistive sensor array was fabricated from SWCNTs noncovalently functionalized with metallo mcxo-tetraphenylporphyrins (Cr(III), Mn(III), Fe(III), Co(III), Co(n), Ni(n), Cu(II), and Zn(II)) [220]. Its responses were treated by statistical analyses and allowed to classify VOCs into five classes alkanes, aromatics, ketones, alcohols, amines. Amines detection as an indicator of meat spoilage was achieved by the same group with the same sensor array [221]. 

Paul-Roth C, Rault-Berthelot J, Simonneaux G, Poriel C, Abdalilah M, Letessier J (2006) Electroactive films of poly(tetraphenylporphyrins) with reduced bandgap. J Electroanal... 

New PHB materials are composed of Zn-tetraben2oporphyrin—aromatic cyanide—poly (methyl methacrylate) (180) or of tetraphenylporphyrin derivatives dispersed in polymer matrices such as PMMA and polyethylene (181). A survey of such materials has been given (181). 

ErQ3 gives both PL and EL emission at 1,500 nm.207-209 Red light (614 nm) is emitted by [Eu(TTFA)3(phen)] (Figure 2(a)) doped in a poly(A-vinylcarbazole) layer.210 The complex [Eu(TTFA)3(TPPO)2] (TPPO = triphenylphosphine oxide, see Figure 2(f)) emits in the red when incorporated in OLEDs,211,212 behavior which is enhanced when the material is heat treated.204 Near-IR EL and PL emission was observed from blends of polyfp-phenylene-vinylene) with [Yb(TPP)(ACAC)] and [Er(TPP)(ACAC)] (H2TPP is 5,10,15,20-tetraphenylporphyrin) by both EL and PL 213... 

The immobilization of the sensitizer and catalyst is especially effective, because contamination of the materials (NBD and QC) with a sensitizer or catalyst markedly lower the efficiency of this system. 4-(N,N-dimethylamino)benzophenone was immobilized on poly(styrene) (30) and silica gel to use it as insoluble sensitizer 101 The polymer pendant sensitizer (30) was much more active than the monomeric compound when used in acetonitrile. Usually, the sensitizing activity of the sensitizer remained almost unchanged through immobilization, but sometimes decreased depending on their structure. As a catalyst of back reaction to release heat, Co(II)-tetraphenylporphyrine was anchored on polystyrene) beads (31), and showed good activity in its immobilized form10Z>. Activity decrease was observed- after several times recyclings of the catalyst. 

The enolate species 2, derived from methacrylates with bulkier ester groups than MMA, are sterically protected against the access of BujAl under the above-mentioned conditions, even when the porphyrin moiety is a non-ortho-substituted tetraphenylporphyrin. An example is shown by the polymerization of ethyl methacrylate (EMA) using 1 (X=Me) as an initiator, where the growing species have an EtO group in the terminal enolate unit 2 (R=Et). After the addition of BujAl to the system, polymerization proceeded to 100% monomer conversion within 10 min. The Mn of the produced polymer was close to the expected value, and the MWD was narrow (Table 5, run 5). A similar result was obtained for the polymerization of isopropyl methacrylate (PMA) with the 1 (X= Mel- soBujAl system, which quantitatively gave a narrow MWD poly(methacr-ylate) with a predicted Mn (Table 5, run 6). 

Harrison, B.S., Foley, T.J., Knefely, A.S., etal. (2004) Near-infrared photo- and electroluminescence of alkoxy-substituted poly(p-phenylene) and nonconjugated polymer/lanthanide tetraphenylporphyrin blends. Chemistry Materials, 16, 2938-2947. 

Some papers have appeared that deal with the use of electrodes whose surfaces are modified with materials suitable for the catalytic reduction of halogenated organic compounds. Kerr and coworkers [408] employed a platinum electrode coated with poly-/7-nitrostyrene for the catalytic reduction of l,2-dibromo-l,2-diphenylethane. Catalytic reduction of 1,2-dibromo-l,2-diphenylethane, 1,2-dibromophenylethane, and 1,2-dibromopropane has been achieved with an electrode coated with covalently immobilized cobalt(II) or copper(II) tetraphenylporphyrin [409]. Carbon electrodes modified with /nc50-tetra(/7-aminophenyl)porphyrinatoiron(III) can be used for the catalytic reduction of benzyl bromide, triphenylmethyl bromide, and hexachloroethane when the surface-bound porphyrin is in the Fe(T) state [410]. Metal phthalocyanine-containing films on pyrolytic graphite have been utilized for the catalytic reduction of P anj -1,2-dibromocyclohexane and trichloroacetic acid [411], and copper and nickel phthalocyanines adsorbed onto carbon promote the catalytic reduction of 1,2-dibromobutane, n-<7/ 5-l,2-dibromocyclohexane, and trichloroacetic acid in bicontinuous microemulsions [412]. When carbon electrodes coated with anodically polymerized films of nickel(Il) salen are cathodically polarized to generate nickel(I) sites, it is possible to carry out the catalytic reduction of iodoethane and 2-iodopropane [29] and the reductive intramolecular cyclizations of 1,3-dibromopropane and of 1,4-dibromo- and 1,4-diiodobutane [413]. A volume edited by Murray [414] contains a valuable set of review chapters by experts in the field of chemically modified electrodes. 

Two older reviews summarize work in this field [124,125]. The following derivatives have been employed as porphyrins Fe(II,III) protoporphyrin-EX (heme, hemin), Fe(II,III) or Co(II) protoporphyrin-IX-diester, chlorophyllins with different metal ions in the core, Fe(II) tetraphenylporphyrin, Mg(II) or Fe(II,III) octaethylporphyrin, Fe(II,III) tetrakis[o-(alkylamido)phenyl]-porphyrin. Polymers with N-donor groups are based on proteins such as poly(L-lysine), poly(L-histidine), poly(Y-benzyl-L-glutamate) or synthetic polymers such as homopolymers and copolymers with vinylpyridine, iV-vinylimidazole or ethyleneimine. 

Bedioui, R, A. Merino, J. Devynck, C.E. Mestres, and C. Bied-Charreton (1988). Poly(pyiTole-manganese tetraphenylporphyrin) flkn electrodes in acetonitrile solution. J. Electroanal. Chem. 239, 433-439. 

Inoue and Takeda reported that the polymerization of propylene oxide at 20 °C with the zinc porphyrin catalyst (Et2Zn/fV-methyl-5,10,15,20-tetraphenylporphyrin, 10) produced syndiotactic poly(propylene oxide) (Af = 31,000, 60% r) (Scheme 24.12). This result was in contrast to those seen for all other zinc-based systems, which afford isotactic poly(propylene oxide). The authors attributed the unexpected syndiotactic microstructure of the polymer to the planar ligand and the isolated nature of the zinc center, which is different than that present in most other zinc aggregate systems." ... 

Le Borgne, A. Spassky, N. Jun, C. L. Momtaz, A. Carbon-13 NMR study of the tacticity of poly(propylene oxide)s prepared by polymerization with a, y, 8-tetraphenylporphyrin/AlEt2Cl as initiator system An example of first-order Markovian statistics in ring-opening polymerization. Makmmol. Chem. 1988,189, 637-650. 

Bedioui F, Merino A, Devynck J, Mestres CE, Bied Charreton C (1988) Poly (p5nrole-manganese tetraphenylporphyrin) film electrodes in acetonitrile solution. J Electroanal Chem 239 433 39... 

Schappacher M, Deffieux A (2011) Reversible switching between linear and ring poly(EO)s bearing iron tetraphenylporphyrin ends triggered by solvent, pH, or redox stimuli. Macro-molecules 44 4503-4510... 

Electrochemical polymerization offers particular advantages in that polymerized porphyrins can form electroactive, adherent and stable films on solid electrodes. Oxidative electropolymerization of several porphyrins and metalloporphyrins have been reported . Special focus has been placed on amino-substituted porphyrins due to the propensity of aniline to form electroactive polymers. Murray et al. reported on the electropolymerization of tetrakis(o-aminophenyl)porphyrin and several para-, ortho-, and meta-substituted tetrakis(aminophenyl)porphyrins with Co as a central metal s. They found that poly-Co(o-NH2)TPP films are effective catalysts for the electroreduction of oxygen in aqueous solution. Metalloporphyrin films on solid electrodes have been mainly characterized by voltammetry and resonsance Raman spectroscopy. The electrochemistry of ruthenium paradiethylamino substituted tetraphenylporphyrins recently have been investigated . This study reports the ac impedance and UV-visible reflectance spectroscopic studies of paradiethylamino substituted tetra-phenylporphyrin films formed via an oxidative electropolymerization process. 

PVP Poly N-vinyl-2-pyrrrolidone CA Cellulose Acetate AR melamine-formaldehyde resin MTD Methyltetracyclododecene EC ethyl cellulose TPP Tetraphenylporphyrin TDCPP 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyinato. 

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