Three series of cobalt(III) corroles were tested as catalysts for the electroreduction dioxygen to water. One was a simple monocorrole represented (Me4Ph5Cor)Co, one face-to-face biscorrole linked by an anthracene (A), biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or dibenzothiophene (S) bridge, (BCY)Co2 (with Y = A, B, X, O S), and bismacrocyclic complex, (PCY)Co2, containing Co(II) porphyrin Co(III) corrole also above rigid spacers (Y O). Cyclic voltammetry rotating ring−disk...

The selective two-electron reduction of dioxygen occurs in the case a monocobalt porphyrin [Co(OEP)], whereas four-electron cofacial dicobalt [Co2(DPX)]. other porphyrins [Co2(DPA), Co2(DPB), and Co2(DPD)] also catalyze dioxygen, but is not as efficient Co2(DPX). μ-superoxo species were produced by reactions dicobalt(II) with presence bulky base subsequent one-electron oxidation resulting μ-peroxo iodine. superhyperfine structure due to two equivalent cobalt nuclei was observed at room...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDouble-decker actinide porphyrins and phthalocyanines. Synthesis spectroscopic characterization of neutral, oxidized, reduced homo- heteroleptic complexesK. M. Kadish, G. Moninot, Y. Hu, D. Dubois, A. Ibnlfassi, J. Barbe, R. GuilardCite this: Am. Chem. Soc. 1993, 115, 18, 8153–8166Publication Date (Print):September 1, 1993Publication History Published online1 May 2002Published inissue 1 September...

The cofacial bisporphyrins H4DPS (DPS = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene), H4DPO (DPO 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzofuran), H4DPX (DPX 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene), H4DPA (DPA 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]anthracene), and H4DPB (DPB...

Steric interactions of the substituents weaken strong NH … N hydrogen bonds (typical for porphycenes) in 1 (R = Me, Et) by increasing distance. As a consequence coordination metal ions, particular Zn2+ is facilitated. These findings can be expected to give impetus research into metalloporphycenes.

pi-pi assisted: Photoinduced electron transfer from cofacial porphyrin dimers to acceptors is prominently accelerated, whereas the back decelerated, relative corresponding monomer (see figure).The radical cation of zinc tetrapentylporphyrin dimerized with an excess neutral counterpart form dimer in which unpaired delocalized over both rings. The dimeric exhibits NIR absorption spectrum characteristic weak pi-bond formation between When dimers, linked by different spacers, are oxidized such...

A free-base cofacial bisporphyrin, H(4)DPOx, forms a pi-complex with acridinium ion (AcH(+)) by pi-pi interaction in benzonitrile (PhCN). Formation of the H(4)DPOx-AcH(+) was probed UV-vis and NMR spectroscopy. The binding constant between AcH(+) H(4)DPOx is determined as 9.7 x 10(4) M(-)(1). Photoinduced electron transfer (ET) from to moiety occurred efficiently form ET state (H(4)DPOx(*)(+)-AcH(*)). successfully detected laser flash photolysis. lifetime 18 mus PhCN at 298 K, quantum yield...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPeroxotitanium(IV) porphyrins. Synthesis, stereochemistry, and propertiesRoger Guilard, Jean Marc Latour, Claude Lecomte, Marchon, Protas, Denis RipollCite this: Inorg. Chem. 1978, 17, 5, 1228–1237Publication Date (Print):May 1, 1978Publication History Published online1 May 2002Published inissue 1 1978https://pubs.acs.org/doi/10.1021/ic50183a027https://doi.org/10.1021/ic50183a027research-articleACS PublicationsRequest reuse permissionsArticle...

A series of biscobalt cofacial porphyrin-corrole dyads bearing mesityl substituents at the meso positions corrole ring were investigated as to their electrochemistry, spectroelectrochemistry, and CO binding properties in nonaqueous media then applied surface a graphite electrode tested electrocatalysts for reduction dioxygen water or hydrogen peroxide air-saturated aqueous solutions containing 1 M HClO(4). The catalytic O(2) with same was also homogeneous phase using 1,1'-dimethylferrocene...

Co(III) corroles were investigated as efficient catalysts for the reduction of dioxygen in presence perchloric acid both heterogeneous and homogeneous systems. The compounds are (5,10,15-tris(pentafluorophenyl)corrole)cobalt (TPFCor)Co, (10-pentafluorophenyl-5,15-dimesitylcorrole)cobalt (F5PhMes2Cor)Co, (5,10,15-trismesitylcorrole)cobalt (Mes3Cor)Co, all which contain bulky substituents at three meso positions corrole macrocycle. Cyclic voltammetry rotating ring-disk electrode used to...

ADVERTISEMENT RETURN TO ISSUEPREVLetterNEXTDiaminoanthraquinone-Linked Polyazamacrocycles: Efficient and Simple Colorimetric Sensor for Lead Ion in Aqueous SolutionElena Ranyuk†, Christiane Morkos Douaihy†, Alla Bessmertnykh†, Franck Denat†, Alexei Averin‡, Irina Beletskaya‡, Roger Guilard†View Author Information Institut de Chimie Moléculaire l'Université Bourgogne (ICMUB), UMR 5260 CNRS, 9 Avenue Alain Savary, BP 47870-21078 Dijon, France, Department of Chemistry, M. V. Lomonosov Moscow...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and characterization of a superoxo complex the dicobalt cofacial diporphyrin [(.mu.-O2)Co2(DPB)(1,5-diphenylimidazole)2][PF6], structure parent Co2(DPB), new synthesis free-base H4(DPB)James P. Collman, James E. Hutchison, Michel Angel Lopez, Alain Tabard, Roger Guilard, Won K. Seok, A. Ibers, Maurice L'HerCite this: J. Am. Chem. Soc. 1992, 114, 25, 9869–9877Publication Date (Print):December 1, 1992Publication History Published online1...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and Characterization of Cofacial Metallodiporphyrins Involving Cobalt Lewis Acid Metals: New Dinuclear Multielectron Redox Catalysts Dioxygen ReductionRoger Guilard, Stephane Brandes, Catherine Tardieux, Alain Tabard, Maurice L'Her, Claudie Miry, Pascal Gouerec, Yasmina Knop, James P. CollmanCite this: J. Am. Chem. Soc. 1995, 117, 47, 11721–11729Publication Date (Print):November 1, 1995Publication History Published online1 May...

A new way to synthesize trans-disubstituted cyclam tetraazamacrocycles 1 is reported. The synthesis proceeds in three steps via the tricyclic 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane system 2, which can be selectively dialkylated and hydrolyzed under basic conditions give final product 1. An understanding of reactivity, based on X-ray experimental electrostatic potential molecular modeling macrotricycle, has permitted elucidation a reaction pathway leading cyclam.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMicellar effects on the aggregation of tetraanionic porphyrins. Spectroscopic characterization free-base meso-tetrakis(4-sulfonatophenyl)porphyrin, (TPPS)H2, and (TPPS)M (M = zinc(II), copper(II), vanadyl) in aqueous micellar mediaKarl M. Kadish, G. B. Maiya, C. Araullo, R. GuilardCite this: Inorg. Chem. 1989, 28, 14, 2725–2731Publication Date (Print):July 1, 1989Publication History Published online1 May 2002Published inissue 1 July...

Immobilisation of Co-salen and Co-fluomine onto ordered mesoporous silica has been achieved through coordination the cobalt to pyridine or imidazole groups covalently attached matrix. Two routes have investigated obtain hybrid materials containing coordinating ligands: post synthesis grafting 4-[2-(trimethoxysilyl)ethyl]pyridine 1 N-trimethoxysilylpropylimidazole 2 on hexagonally via SiOH direct method i.e. co-hydrolysis polycondensation same functionalised organotrimethoxysilane with a...

Copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, UV–visible spectroscopy. Three crystalline forms were grown studied X-ray diffraction methods (single crystal powder). The highly electron-withdrawing effect phosphoryl groups attached directly to the porphyrin macrocycle results in a self-assembling process, with formation stable 2D coordination network,...