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Roger Guilard

Publications and source records attributed to Roger Guilard.

At least 19 recordsLinked to original sources
PubMed2007

Modulation of the singlet-singlet through-space energy transfer rates in cofacial bisporphyrin and porphyrin-corrole dyads.

A new series of relatively flexible cofacial donor-acceptor dyads for singlet-singlet energy transfer with the corrole or etio-porphyrin free base and zinc porphyrin as the acceptor and donor, respectively, were synthesized and characterized (represented as (PMes2COx)ZnH3 (13), (PMes2CO)ZnH3 (14), and (PMes2CX)ZnH3 (15)) where (PMes2COx = [2-[5-(5,15-dimesitylcorrol-10-yl)-diphenylether-2'-yl]-13,17-diethyl-2,3,7,8,12,18-hexamethylporphyrin]), (PMes2CO = [5-[5-(5,15-dimesitylcorrol-10-yl)-dibenzofuran-4-yl]-13,17-diethyl-2,3,7,8,12,18-hexamethylporphyrin]), and (PMes2CX = [5-[5-(5,15-dimesitylcorrol-10-yl)-9,9-dimethylxanthen-4-yl)]-13,17-diethyl-2,3,7,8,12,18-hexamethylporphyrin]), respectively) along with the homobismacrocycles (DPOx)ZnH2 (17) and (DPOx)Zn2 (18) (where (DPOx = 2,2'-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]diphenylether) as comparison standards. The rate for energy transfer (kET) extracted by the measurements of fluorescence lifetimes are of the same order of magnitude as those recently reported for the rigidly held face-to-face dyads ((DPB)ZnH2 (1), (DPX)ZnH2 (2), (DPA)ZnH2 (3), (DPO)ZnH2 (4), and (DPS)ZnH2 (5) where (DPB = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene), (DPX = 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene), (DPA = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]anthracene), (DPO = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzofuran), and (DPS = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene), respectively), but for the first time, it is shown that the presence of a bulky group located between the acceptor and the donor moiety influences the transfer rate. The presence of perpendicular mesityl groups on the acceptor macrocycle prevents the two macrorings from interacting strongly; therefore, kET is slower. On the other hand, by rendering the rigid spacer flexible (i.e., changing the dibenzofuran rigid spacer to the flexible diphenylether assembling fragment), kET increases due to stronger intermacrocycle interactions. This study is complemented by DFT computations (B3LYP/3-21G*) as a molecular modeling tool where subtle structural features explain the changes in kET. During the course of this study, X-ray structures of 17 and 18 were investigated and exhibit a linear stacking of the bismacrocycles where intermolecular porphyrin-porphyrin interactions are observed (dinter(Zn...Zn) = 4.66 and 4.57 A, for 17 and 18, respectively).

Computer Simulation↗
PubMed2007

Selective chemisorption of carbon monoxide by organic-inorganic hybrid materials incorporating cobalt(III) corroles as sensing components.

Twenty-one hybrid materials incorporating cobalt(III) corrole complexes were synthesized by a sol-gel process or by grafting the metallocorrole onto a mesostructured silica of the SBA-15 type. All the materials show an almost infinite selectivity for carbon monoxide with respect to dinitrogen and dioxygen in the low-pressure domain where the chemisorption phenomenon is predominant. This peculiar property is of prime importance for an application as a CO sensor. The selectivity slightly decreases at high pressures where nonselective physisorption phenomena mainly occur. The percentage of active sites for CO chemisorption ranges from 22 to 64 %. This low percentage may be attributable to interactions between the cobalt(III) corroles with silanol or siloxane groups remaining at the surface of the materials which prevent further coordination of the CO molecule. Notably, the most efficient materials are those prepared in the presence of a protecting ligand (pyridine) during the gelation or the grafting process. The removal of this ligand after the gelation process releases a cavity around the cobalt ion that favors the coordination of a carbon monoxide molecule. The CO adsorption properties of the SBA-15 hybrid were not affected over a period of several months thus indicating a high stability of the material. Conversely, the xerogel capacities slowly decrease owing to the evolution of the material structure.

Adsorption↗
PubMed2007

Exceptional affinity of nanostructured organic-inorganic hybrid materials towards dioxygen: confinement effect of copper complexes.

We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2) adsorption; this is induced by close confinement of the two copper ions leading to end-on mu-eta(1):eta(1)-peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic-inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu(2) (I,I) species can be regenerated after several adsorption-desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.

Adsorption↗
PubMed2006

Persistent electron-transfer state of a pi-complex of acridinium ion inserted between porphyrin rings of cofacial bisporphyrins.

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(+) pi-complex was probed by UV-vis and NMR spectroscopy. The binding constant between AcH(+) and H(4)DPOx is determined as 9.7 x 10(4) M(-)(1). Photoinduced electron transfer (ET) from the H(4)DPOx to the AcH(+) moiety occurred efficiently in the pi-complex to form the ET state (H(4)DPOx(*)(+)-AcH(*)). The ET state is successfully detected by laser flash photolysis. The lifetime of the ET state is 18 mus in PhCN at 298 K, and the quantum yield of the ET state is 90%. The temperature dependence of the ET state lifetime has been examined in the range from 273 to 353 K. The ET state lifetime exhibited a large temperature dependence, and the linear plot of ln(k(BET)T(1/2)) vs T(-)()(1), in accordance with the Marcus equation, affords the ET reorganization energy (0.54 eV). As a result, a remarkably long-lived ET state has been attained at low temperature, and virtually no decay of the ET state was observed at 77 K. Such an extremely long-lived ET state is indeed detected by steady-state UV-vis absorption spectroscopy.

Journal Article↗
PubMed2006

Cobalt(IV) corroles as catalysts for the electroreduction of O2: reactions of heterobimetallic dyads containing a face-to-face linked Fe(III) or Mn(III) porphyrin.

A series of heterobinuclear cofacial porphyrin-corrole dyads containing a Co(IV) corrole linked by one of four different spacers in a face-to-face arrangement with an Fe(III) or Mn(III) porphyrin have been examined as catalysts for the electroreduction of O(2) to H(2)O and/or H(2)O(2) when adsorbed on the surface of a graphite electrode in air-saturated aqueous solutions containing 1M HClO(4). The examined compounds are represented as (PCY)M(III)ClCo(IV)Cl where P is a porphyrin dianion, C is a corrole trianion and Y is a biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or anthracene (A) spacer. The catalytic behavior of the seven investigated dyads in the two heterobimetallic (PCY)MClCoCl series of catalysts is compared on one hand to what was previously reported for related dyads with a single Co(III) corrole macrocycle linked to a free-base porphyrin with the same set of linking bridges, (PCY)H(2)Co, and on the other hand to dicobalt porphyrin-corrole dyads of the form (PCY)Co(2) which were shown to efficiently electrocatalyze the four electron reduction of O(2) at a graphite electrode in acid media. Comparisons between the four series of porphyrin-corrole dyads, (PCY)Co(2), (PCY)H(2)Co, (PCY)FeClCoCl and (PCY)MnClCoCl, show that in all cases the biscobalt dyads catalyze O(2) electroreduction at potentials more positive by an average 110mV as compared to the related series of compounds containing a Co(III) or Co(IV) corrole macrocycle linked to a free-base metalloporphyrin or a metalloporphyrin with an Fe(III) or Mn(III) central metal ion. The data indicates that the E(1/2) values where electrocatalysis is initiated is related to the initial site of electron transfer, which is the Co(III)/Co(II) porphyrin reduction process in the case of (PCY)Co(2) and the Co(IV)/Co(III) corrole reduction in the case of (PCY)MnClCoCl, (PCY)FeClCoCl and (PCY)H(2)Co. The overall data also suggests that the catalytically active form of the biscobalt dyad in (PCY)Co(2) contains a Co(II) porphyrin and a Co(IV) corrole.

Binding Sites↗
PubMed2005

Synthesis and photophysical properties of meso-substituted bisporphyrins: comparative study of phosphorescence quenching for dioxygen sensing.

The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex.

Luminescence↗
PubMed2005

Electrochemistry and spectroelectrochemistry of heterobimetallic porphyrin-corrole dyads. Influence of the spacer, metal ion, and oxidation state on the pyridine binding ability.

Combined electrochemical and UV-visible spectroelectrochemical methods were utilized to elucidate the prevailing mechanisms for electroreduction of previously synthesized porphyrin-corrole dyads of the form (PCY)H2Co and (PCY)MClCoCl where M = Fe(III) or Mn(III), PC = porphyrin-corrole, and Y is a bridging group, either biphenylenyl (B), 9,9-dimethylxanthenyl (X), anthracenyl (A), or dibenzofuranyl (O). These studies were carried out in pyridine, conditions under which the cobalt(IV) corrole in (PCY)MClCoCl is immediately reduced to its Co(III) form, thus enabling direct comparisons with the free-base porphyrin dyad, (PCY)H2Co(III) under the same solution conditions. The compounds are all reduced in multiple one-electron-transfer steps, the first of which involves the M(III)/M(II) process of the porphyrin in the case of (PCY)MClCoCl and the Co(III)/Co(II) process of the corrole in the case of (PCY)H2Co. Each metal-centered redox reaction may be accompanied by the gain or loss of pyridine axial ligands, with the exact stoichiometry of the exchange process depending upon the specific combination of metal ions in the dyad, their oxidation states, and the particular spacer in the complex. Before this study was started, it was expected that the porphyrin-corrole dyads with the largest spacers, namely, O and A, would readily accommodate the formation of cobalt(III) bis-pyridine adducts because of the larger size of the cavity while dyads with the smallest B spacer would seem to have insufficient room to add even a single pyridine within the cavity, as was structurally seen in the case of (PCB)H2Co(py). This is clearly not the case, as shown in the present study. A reversible Co(III)/Co(II) reaction is seen for (PCB)MnClCoCl at -0.62 V, which when combined with spectroscopic data, leads to the assignment of (PCB)Mn(III)(py)2Co(III)(py) as the species in pyridine. The reduction of (PCB)Mn(III)(py)2Co(III)(py) to (PCB)Mn(II)(py)Co(III)(py) is accompanied on the slower spectroelectrochemical time scale by the appearance of a 603 nm band in the UV-vis spectra and is consistent with the addition of a second pyridine ligand to the Co(III)(py) unit of the dyad as one ligand is lost from the electrogenerated manganese(II) porphyrin, thus maintaining one pyridine ligand within the cavity. A different change in the coordination number is observed in the case of (PCB)FeClCoCl. Here the initial Fe(III) complex can be assigned as (PCB)Fe(III)ClCo(III)(py), which has no pyridine molecule within the cavity and the singly reduced form is characterized as (PCB)Fe(II)(py)2Co(III)(py)2, which contains two pyridine ligands inside the cavity. A following one-electron reduction of the Fe(II)/Co(III) complex then gives [(PCB)Fe(II)(py)2Co(II)]-.

Journal Article↗
PubMed2005

Synthesis, characterization, and x-ray crystal structures of cyclam derivatives. 8. Thermodynamic and kinetic appraisal of lead(II) chelation by octadentate carbamoyl-armed macrocycles.

En route toward the development of hybrid organic-inorganic extracting materials incorporating lead-selective chelators and their implementation in water purification processes, the lead(II) binding properties of three N-carbamoylmethyl-substituted 1,4,8,11-tetraazacyclotetradecanes (cyclams) have been fully investigated by spectroscopic (IR, UV-vis, MALDI-TOF MS, (1)H and (13)C NMR), X-ray crystallographic, potentiometric, and kinetic methods. Solution NMR studies revealed that the Pb(2+) ion is entrapped in a molecular cage constituted by the four macrocyclic nitrogen and four amidic oxygen atoms. Protonation and lead binding constants determined in aqueous solution were shown to be linearly dependent, so that all three derivatives possess a similar affinity at any pH value. Thermodynamic and kinetic parameters revealed the crucial role played by the intramolecular hydrogen bonds also evidenced in the crystal structure of the tetraacetamide derivative L(1), which involve the lone pair of each macrocyclic tertiary amine and one amidic hydrogen atom belonging to the appended arm. In contrast to L(1), the absence of such intramolecular interactions for N-(dimethyl)carbamoylmethyl- and N-(diethyl)carbamoylmethyl-substituted cyclams (L(2) and L(3), respectively) accounts for the 2-3 orders of magnitude enhancement of their proton and lead binding affinities. Stopped-flow kinetic measurements enabled unraveling the formation process of the three lead(II) complexes that proceeds in a single rate-limiting step according to the Eigen-Winkler mechanism, while the apparent rate constants were found to increase in the order L(3) < L(2) << L(1) as a consequence of the more acidic character of L(1). A common proton-assisted dissociation mechanism has been found for the three lead(II) complexes, which involves the rapid formation of a protonated, six-coordinate intermediate followed by either a unimolecular decomposition or a bimolecular attack of a second hydronium ion.

Carbamates↗
PubMed2005

Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads.

Three face-to-face linked porphyrin-corrole dyads were investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. The same three compounds were also investigated as to their ability to catalyze the electroreduction of dioxygen in aqueous 1 M HClO4 or HCl when adsorbed on a graphite electrode. The characterized compounds are represented as (PCY)H2Co, where P = a porphyrin dianion; C = a corrole trianion; and Y = a biphenylenyl, 9,9-dimethylxanthenyl, or anthracenyl spacer, which links the two macrocycles in a face-to-face arrangement. An axial binding of one or two Cl- ligands to the cobalt center of the corrole is observed for singly and doubly oxidized (PCY)H2Co, with the exact stoichiometry of the reaction depending upon the spacer size and the concentration of Cl- added to solution. No Cl- binding occurs for the neutral or reduced forms of the dyad, which contrasts with what is seen for the monocorrole, (Me4Ph5Cor)Co, where a single Cl- ligand is added to the Co(III) corrole in PhCN. The Co(III) form of the corrole in (PCY)H2Co also appears to be the catalytically active species in the electroreduction of dioxygen, which occurs at potentials associated with the Co(IV)/Co(III) reaction, that is, 0.35 V in 1 M HClO4 as compared to 0.31-0.42 V for the same three dyads in PhCN and 0.1 M TBAP. The potential for the catalytic electroreduction of O2 in HCl shifts negatively by 60 to 70 mV as compared to E(1/2) values in 1 M HClO4, consistent with the binding of Cl- to the Co(IV) form of the corrole and its rapid dissociation after electroreduction to Co(III) at the electrode surface.

Journal Article↗
PubMed2005

Regioselective N-functionalization of tetraazacycloalkanes.

[reaction: see text] Bisaminal type compounds obtained by condensation of pyruvic aldehyde with the suitable open-chain tetraamine followed by cyclization with either dibromoethane or dibromopropane can be regioselectively quaternized by a wide range of alkylating agents. Removal of the bisaminal bridge yields the monosubstituted tetraazamacrocycle or bismacrocycle. Further functionalization allows the preparation of bifunctional ligands or trisubstituted macrocycles. The structure of six compounds was solved by X-ray diffraction, and the unexpected results are rationalized according to the molecular modeling calculations.

Journal Article↗
PubMed2005

Heterobimetallic complexes of cobalt(IV) porphyrin-corrole dyads. Synthesis, physicochemical properties, and X-ray structural characterization.

The synthesis of a novel family of heterobinuclear cofacial biphenylene (B), anthracene (A), 9,9-dimethylxanthene (X), or dibenzofuran (O) bridged porphyrin-corrole complexes, (PCY)MClCoCl, is reported, M being either an iron(III) or manganese(III) ion. Each complex was characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy. Unlike previously examined biscobalt porphyrin-corrole dyads, the cobalt ion of the corrole moiety is present in a high-valence +4 oxidation state, as proven by electrochemistry, spectroelectrochemistry, and an X-ray diffraction study of (PCB)FeClCoCl, which shows the presence of a bound Cl- anion on the cobalt corrole. Structural data: (PCB)FeClCoCl x 0.5(C7H16) x 0.5(CH2Cl2) x 2H2O, triclinic, space group P1, a = 13.8463(3) A, b = 16.8164(5) A, c = 17.9072(6) A, alpha = 93.780(1) degrees, beta = 111.143(1) degrees, gamma = 97.463(2) degrees, Z = 2.

Journal Article↗
PubMed2005

Triplet-triplet energy transfer controlled by the donor-acceptor distance in rigidly held palladium-containing cofacial bisporphyrins.

Eleven new complexes, including mono-, heterobi-, and homobimetallic cofacial bisporphyrins, (Pd)H2DPS, (M)H2DPX, (M)H2DPB, (PdZn)DPS, (PdZn)DPX, (Pt)2DPX, (M)2DPB (M = Pd, Pt), and (Pt)P (DPS4- = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX(4-) = 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, DPB4- = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion, P2- = 5-phenyl-2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin dianion) have been synthesized and characterized. The photophysical properties of the donor (M)P (M=Pd or Pt, P=porphyrin chromophore) and the acceptor (free base H(2)P or (Zn)P) depend on the C(meso)-C(meso) distance and the presence of a heavy atom such as Pd(II) or Pt(II). The data were compared with those for the known compounds (Pd)2DPS, (Pd)2DPX, H4DPS, H4DPX, H4DPB, (Pd)P, (Zn)P, and H(2)P. The rate constants for triplet-triplet energy transfer (k(ET)) were measured for the heterobimetallic (PdZn) and monometallic [(M)H2] derivatives (M=Pd, Pt). The fluorescence lifetimes (Deltatau(F)) of the acceptors decrease as a result of the heavy-atom effect, and vary as follows: (Pd)H2DPS<<(Pd)H2DPX approximately (Pd)H2DPB. The k(ET) values calculated according to the equation k(ET)=(1/tau(emi)-1/tau(emi) (0)), where tau(emi) (0) is the emission lifetime of the homobimetallic bisporphyrins (no ET occurs), are equal to 0, 247+/-57 and 133+/-52 s(-1) for DPS, DPX, and DPB, respectively, in the (Pd)H(2) series. These measurements allowed the range of distance over which the Dexter mechanism for T(1)-T(1) energy transfer ceases to operate to be determined. This distance is somewhere between 4.3 and 6.3 A, in agreement with our recent findings on singlet-singlet energy transfer. During the course of this study, the X-ray crystal structure for (Pd)H2DPX was obtained; triclinic (P1), a = 11.1016(1), b = 14.9868(2), c = 20.6786(3) A, alpha = 102.091(1), beta = 100.587(1), gamma = 101.817(1) degrees , V = 3199.19(7) A(3), Z = 2.

Crystallography, X-Ray↗
PubMed2005

Cobalt(III) corroles as electrocatalysts for the reduction of dioxygen: reactivity of a monocorrole, biscorroles, and porphyrin-corrole dyads.

Three series of cobalt(III) corroles were tested as catalysts for the electroreduction of dioxygen to water. One was a simple monocorrole represented as (Me(4)Ph(5)Cor)Co, one a face-to-face biscorrole linked by an anthracene (A), biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or dibenzothiophene (S) bridge, (BCY)Co(2) (with Y = A, B, X, O or S), and one a face-to-face bismacrocyclic complex, (PCY)Co(2), containing a Co(II) porphyrin and a Co(III) corrole also linked by one of the above rigid spacers (Y = A, B, X, or O). Cyclic voltammetry and rotating ring-disk electrode voltammetry were both used to examine the catalytic activity of the cobalt complexes in acid media. The mixed valent Co(II)/Co(III) complexes, (PCY)Co(2), and the biscorrole complexes, (BCY)Co(2), which contain two Co(III) ions in their air-stable forms, all provide a direct four-electron pathway for the reduction of O(2) to H(2)O in aqueous acidic electrolyte when adsorbed on a graphite electrode, with the most efficient process being observed in the case of the complexes having an anthracene spacer. A relatively small amount of hydrogen peroxide was detected at the ring electrode in the vicinity of E(1/2) which was located at 0.47 V vs SCE for (PCA)Co(2) and 0.39 V vs SCE for (BCA)Co(2). The cobalt(III) monocorrole (Me(4)Ph(5)Cor)Co also catalyzes the electroreduction of dioxygen at E(1/2) = 0.38 V with the final products being an approximate 50% mixture of H(2)O(2) and H(2)O.

Journal Article↗
PubMed2005

Synthesis, characterization, and photophysical properties of a free base and a biszinc(II) complex of 1,3-bisporphyrincalix[4]arene: evidence for "tunable intramolecular open and closed conformations".

The bismacrocycle 5,17-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-25,26,27,28-tetrapropoxycalix[4]arene (4) was synthesized in three steps from the corresponding bisaldehyde 5,17-diformyl-25,26,27,28-tetrapropoxycalix[4]arene. The biszinc(II) complex (5) was prepared as well, and the photophysical properties were measured using 2-MeTHF as solvent at 298 and 77 K. While computer modeling for 5 predicts that both pinched cone conformers, closed (porphyrins near each other) and open (porphyrins away from each other), may exist in the "gas phase", the experimental data indicate clearly that no zinc porphyrin...zinc porphyrin interactions are present in solution at 298 K, favoring the open conformer, where the two macrocycles are placed away from each other. On the other hand, clear evidence for a closed conformer is observed at 77 K. Variable-temperature (1)H NMR experiments show that 5 is fluxional between 298 and 183 K, while 4 keeps the open conformation for the whole temperature range. This behavior is unprecedented for calix[4]areneporphyrin compounds, and the relative porphyrin ring rigidity is postulated to explain this difference.

Journal Article↗
PubMed2004

Dehydrogenation versus oxygenation in two-electron and four-electron reduction of dioxygen by 9-alkyl-10-methyl-9,10-dihydroacridines catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins in the presence of perchloric acid.

Dehydrogenation of 10-methyl-9,10-dihydroacridine (AcrH(2)) by dioxygen (O(2)) proceeds efficiently, accompanied by the two-electron and four-electron reduction of O(2) to produce H(2)O(2) and H(2)O, which are effectively catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins in the presence of perchloric acid (HClO(4)) in acetonitrile (MeCN) and benzonitrile (PhCN), respectively. The cobalt porphyrin catalyzed two-electron reduction of O(2) also occurs efficiently by 9-alkyl-10-methyl-9,10-dihydroacridines (AcrHR; R = Me, Et, and CH(2)COOEt) to yield 9-alkyl-10-methylacridinium ion (AcrR+) and H(2)O(2). In the case of R = Bu(t) and CMe(2)COOMe, however, the catalytic two-electron and four-electron reduction of O(2) by AcrHR results in oxygenation of the alkyl group of AcrHR rather than dehydrogenation to yield 10-methylacridinium ion (AcrH+) and the oxygenated products of the alkyl groups, i.e., the corresponding hydroperoxides (ROOH) and the alcohol (ROH), respectively. The catalytic mechanisms of the dehydrogenation vs the oxygenation of AcrHR in the two-electron and four-electron reduction of O(2), catalyzed by monomeric cobalt porphyrins and cofacial dicobalt porphyrins, respectively, are discussed in relation to the C(9)-H or C(9)-C bond cleavage of AcrHR radical cations produced in the electron-transfer oxidation of AcrHR.

Acridines↗