0000000000021352
AUTHOR
Maya El Ojaimi
showing 11 related works from this author
Clarification of the oxidation state of cobalt corroles inheterogeneous and homogeneous catalytic reduction of dioxygen
2008
Co(III) corroles were investigated as efficient catalysts for the reduction of dioxygen in the presence of perchloric acid in both heterogeneous and homogeneous systems. The investigated compounds are (5,10,15-tris(pentafluorophenyl)corrole)cobalt (TPFCor)Co, (10-pentafluorophenyl-5,15-dimesitylcorrole)cobalt (F 5PhMes 2Cor)Co, and (5,10,15-trismesitylcorrole)cobalt (Mes 3Cor)Co, all of which contain bulky substituents at the three meso positions of the corrole macrocycle. Cyclic voltammetry and rotating ring-disk electrode voltammetry were used to examine the catalytic activity of the compounds when adsorbed on the surface of a graphite electrode in the presence of 1.0 M perchloric acid, a…
Electrochemistry and spectroelectrochemistry of bismanganese biscorroles dyads
2011
Three manganese biscorrole dyads were synthesized, physicochemically characterized and investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous media. Each dyad contained the same two corroles linked in a face-to-face arrangement via one of the three different linking groups, 9,9-dimethylxanthene, anthracene or diphenylether, the exact nature of which determined the distance and possible interaction between the two metallomacrocycles. The initial compounds contained Mn ( III ) in their air stable form and were shown to exhibit two major redox processes, one being a Mn (III)/ Mn (IV) conversion and the other being either Mn ( III )/ Mn ( II ) or reduction at the c…
Face-to-face held Pacman type porphyrin-fullerene dyads: design, synthesis, charge transfer interactions and photophysical studies
2008
Pacman-type face-to-face zinc-porphyrin-fullerene dyads have been newly synthesized and studied. Owing to the close proximity of the donor and acceptor entities, strong pi-pi intramolecular interactions between the porphyrin and fullerene entities resulted in modulating the spectral and electrochemical properties of the dyads. New absorption and emission bands that correspond to the charge-transfer interactions were observed in the near-IR region. Time-resolved transient absorption studies revealed efficient photoinduced electron transfer from the singlet excited porphyrin to the fullerene entity. The rate constants for photoinduced electron transfer are analyzed in terms of the Marcus theo…
Through space singlet-singlet and triplet-triplet energy transfers in cofacial bisporphyrins held by the carbazoyl spacer
2007
The through space singlet-singlet and triplet-triplet energy transfers in cofacial bis(etio-porphyrins) rigidly held by the carbazoyl spacer were investigated. The studies on singlet-singlet transfer, which operates via a Förster mechanism, were performed using the zinc porphyrin and free base chromophores as energy donor and acceptor, respectively, while the investigation on triplet-triplet processes was performed using the palladium porphyrin, and the zinc porphyrin and free base chromophores as donor and acceptors, respectively. The rate for singlet-singlet transfer ( k ET ( singlet )) is unexpectedly slower than that reported for other similar, rigidly held bisporphyrins such as H 2( D…
Dynamics of closure of zinc bis-porphyrin molecular tweezers with copper(II) ions and electron transfer.
2011
Zinc bis-porphyrin molecular tweezers composed of a N(4) spacer bound through pyridyl units to the meso position of porphyrins were synthesized, and the tweezers are closed by the coordination of a copper(II) ion inside the spacer ligand. The effect of the π-π interaction between the porphyrin rings in the closed conformation on the absorption spectra of multi-electron oxidized species and the reduction potentials were clarified by chemical and electrochemical oxidation of the closed form of the zinc bis-porphyrin molecular tweezers in comparison with the open form without copper(II) ion and the corresponding porphyrin monomer. The shifts in redox potentials and absorption spectrum of the p…
Solvent, anion and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles
2008
A series of manganese(III) corroles were investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous solvents. Up to three oxidations and one reduction were obtained for each complex depending on the solvents. The main compound discussed in this paper is the meso-substituted manganese corrole, (Mes 2PhCor)Mn, and the main points are how changes in axially coordinated anion and solvent will affect the redox potentials and UV-vis spectra of each electrogenerated species in oxidation states of Mn(III), Mn(IV), or Mn(II). The anions OAc (-), Cl (-), CN (-), and SCN (-) were found to form five-coordinate complexes with the neutral Mn(III) corrole while two OH (-) or F (-)…
Energy transfers in monomers, dimers, and trimers of zinc(II) and palladium(II) porphyrins bridged by rigid Pt-containing conjugated organometallic s…
2009
A series of linear monomers (spacer-M(P)), dimers (M(P)-spacer-M'(P)), and trimers (M(P)-spacer-M'(P)-spacer-M(P)) of spacer/metalloporphyrin systems (M' = Zn, M = Zn, Pd, P = porphyrin, and spacer = trans-C(6)H(4)C[triple bond]CPtL(2)C[triple bond]CC(6)H(4)- (L = PEt(3))) including mixed metalloporphyrin compounds, were synthesized and characterized. The S(1) and T(1) energy transfers Pd(P)*--Zn(P) occur with rates of approximately 2 x 10(9) s(-1), S(1), and 0.15 x 10(3) (slow component) and 4.3 x 10(3) s(-1) (fast component), T(1). On the basis of a literature comparison with a related dyad, the Pt atom in the conjugated chain slows down the transfers. The excitation in the absorption ban…
Efficient two-step synthesis of face-to-face meso-substituted bis(corrole) dyads
2008
The synthesis of face-to-face meso-substituted bis(corrole) systems was revisited. By using a new synthetic pathway, the reaction was generalized to any type of linker and the yield was considerably increased. The dyads were obtained in yields up to 20 % from a dialdehyde linker and dipyrromethane in a one-step reaction. The best reaction conditions required a decreased amount of TFA catalyst (1.4 equiv.) and a large excess of dipyrromethane (up to 8 equiv). Under these conditions, four bis(corrole)s linked by 2,2′-diphenyl ether, 9,9-dimethylxanthene, anthracene, and dibenzofuran spacers were synthesized.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Electrochemistry and Spectroelectrochemistry of Bismanganese Porphyrin-Corrole Dyads
2011
A series of homobimetallic manganese cofacial porphyrin-corrole dyads were synthesized and investigated as to their electrochemistry, spectroelectrochemistry, and ligand binding properties in nonaqueous media. Four dyads were investigated, each of which contained a Mn(III) corrole linked in a face-to-face arrangement with a Mn(III) porphyrin. The main difference between compounds in the series is the type of spacer, 9,9-dimethylxanthene, anthracene, dibenzofuran, or diphenylether, which determines the distance and interaction between the metallomacrocycles. Each redox process of the porphyrin-corrole dyads was assigned on the basis of spectroscopic and electrochemical data and by comparison…
Catalytic activity of biscobalt porphyrin-corrole dyads toward the reduction of dioxygen
2009
A series of biscobalt cofacial porphyrin-corrole dyads bearing mesityl substituents at the meso positions of the corrole ring were investigated as to their electrochemistry, spectroelectrochemistry, and CO binding properties in nonaqueous media and then applied to the surface of a graphite electrode and tested as electrocatalysts for the reduction of dioxygen to water or hydrogen peroxide in air-saturated aqueous solutions containing 1 M HClO(4). The catalytic reduction of O(2) with the same dyads was also investigated in the homogeneous phase using 1,1'-dimethylferrocene as a reductant in PhCN containing HClO(4). The examined compounds are represented as (PMes(2)CY)Co(2), where P = a porph…
Towards the synthesis of substituted porphyrins by a pyridyl group bearing a reactive functionality
2010
Pyridyl-substituted porphyrins bearing a reactive functionality were prepared via Suzuki cross-coupling reactions and resulted in very good yields. These compounds are precursors of new porphyrin architectures able to coordinate two metals: one in the porphyrin core and the second around the pyridyl moiety. During the coupling reactions, a higher reactivity of a chloro picolyl group was evidenced compared to a bromo function on the same reacting molecule.