Meso Carbon Research Articles

Synthesis and Anion‐Binding Studies of Thiaphlorins and Covalently Linked Thiaphlorin–Porphyrin Dyads

AbstractA series of thiaphlorins with N2S2 and N3S cores have been prepared in decent yields from readily available precursors. The thiaphlorins were characterized by all spectroscopic techniques and the structures of two thiaphlorins were solved by X‐ray crystallography. The spectral studies indicated that the properties of thiaphlorins were quite different from those of thiaporphyrins. The methodology used for the synthesis of thiaphlorins has been extended to synthesize a series of monofunctionalized thiaphlorins. We also performed functional group transformation of thiaphlorins without decomposition, supporting the conjecture of the stable natures of thiaphlorins. The crystal structure analysis of two thiaphlorins indicated that the macrocycles are not planar and that they each show a marked kink at sp3‐hybridised meso carbon. The functionalized thiaphlorins have been used to synthesize several novel porphyrin–thiaphlorin dyads as well as a bis(thiaphlorin) dyad under mild palladium(0) coupling conditions. Preliminary anion‐binding studies carried out on thiaphlorins and porphyrin–thiaphlorin dyads indicated that they can bind anions effectively in their protonated forms and that these systems can also be used as optical sensors.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Structural Diversity in Expanded Porphyrins

Inspired by the chemistry of porphyrins, in the last decade, a new research area where porphyrin analogues such as expanded, isomeric, and contracted porphyrins have been synthesized, and their chemistry has been exploited extensively. Expanded porphyrins are macrocyclic compounds where pyrrole or heterocyclic rings are connected to each other through meso carbon bridges. Depending on the number of pyrrole rings in conjugation or the number of double bonds linking the four pyrrole rings expanded porphyrins containing up to 64 pi electrons are reported in the literature. The interest in these systems lies in their potential applications as anion binding agents, as photosensitizers for photodynamic therapy (PDT), in antisensing applications, as MRI contrasting agents, and more recently, as material for nonlinear optical application. Expanded porphyrins containing more than four pyrrole or heterocyclic rings, such as sapphyrin (five pyrrole), rubyrin (six pyrrole), heptaphyrin (seven pyrrole), and octaphyrin (eight pyrrole), are reported in the literature. Furthermore, substituents on expanded porphyrins can be attached either at the meso carbons or at beta-pyrrole positions. beta-substituted expanded porphyrins generally adopt normal structure where all the pyrrole nitrogens point inward in the cavity 1, while the meso-substituted expanded porphyrins exhibit normal 2, inverted 3, fused 4, confused 5, and figure eight 6 conformations. The conformation of expanded porphyrin is dependent on the nature of the linkage of the heterocyclic rings, the nature and the number of the heteroatoms present in the cavity, and the state of protonation. It is possible to change one conformation to another by varying temperature or by simple chemical modification, such as protonation by acids. An understanding of the structure-function correlation in expanded porphyrins is an important step for designing these molecules for their potential applications. In this context, even though several meso aryl expanded porphyrins are reported in literature, there is no comprehensive understanding of structural diversity exhibited by them. In this Account, an attempt has been made to provide a systematic understanding of the conditions and circumstances that lead to various conformations and structures. Specifically, the structural diversities exhibited by five pyrrolic macrocycles to ten pyrrolic macrocycles are covered in this Account. In pentapyrrolic systems, sapphyrins, N-fused, and N-confused pentaphyrins are described. It has been shown that the positions of the heteroatom affect the conformation and in turn the aromaticity. In hexapyrrolic systems, rubyrins and hexaphyrins are covered. The conformation of core-modified rubyrins was found to be dependent on the number and nature of the heteroatom present inside the core. Further, in the hexapyrrolic systems, an increase in the number of meso carbons from four (rubyrin) to six (hexaphyrin) increases the conformational flexibility, where different types of conformations are observed upon going from free base to protonated form. Heptapyrrolic and octapyrrolic expanded porphyrins also exhibit rich structural diversity. Octaphyrins are known to exhibit figure eight conformation, where the macrocycle experiences a twist at the meso carbon, losing aromatic character. By suitable chemical modification, it is possible to avoid the twist, and planar 34 pi core-modified octaphyrins have been reported that show aromatic character and obey the (4 n + 2) Hückel rule. The structural diversity exhibited by nine pyrrolic macrocycles (nonaphyrins) and ten pyrrolic macrocycles (decaphyrins) are also described.

Theoretical insight into the hydroxylamine oxidoreductase mechanism

The multiheme enzyme hydroxylamine oxidoreductase from the autotrophic bacteria Nitrosomonas europaea catalyzes the conversion of hydroxylamine to nitrite, with a complicate arrangement of heme groups in three subunits. As a distinctive feature, the protein has a covalent linkage between a tyrosyl residue of one subunit and a meso carbon atom of the heme active site of another. We studied the influence of this bond in the catalysis from a theoretical perspective through electronic structure calculations at the density functional theory level, starting from the crystal structure of the protein. Geometry optimizations of proposed reaction intermediates were used to calculate the dissociation energy of different nitrogen containing ligands, considering the presence and absence of the meso tyrosyl residue. The results indicate that the tyrosine residue enhances the binding of hydroxylamine, and increases the stability of a FeIIINO intermediate, while behaving indifferently in the FeIINO form. The calculations performed on model systems including neighboring aminoacids revealed the probable formation of a bidentate hydrogen bond between the FeIIIH2O complex and Asp 257, in a high-spin aquo complex as the resting state. Characterization of non-planar heme distortions showed that the meso-substituent induces significant ruffling in the evaluated intermediates.

Metal−Porphyrin Orbital Interactions in Highly Saddled Low-Spin Iron(III) Porphyrin Complexes

Substituent effects of the meso-aryl (Ar) groups on the 1H and 13C NMR chemical shifts in a series of low-spin highly saddled iron(III) octaethyltetraarylporphyrinates, [Fe(OETArP)L2]+, where axial ligands (L) are imidazole (HIm) and tert-butylisocyanide ((t)BuNC), have been examined to reveal the nature of the interactions between metal and porphyrin orbitals. As for the bis(HIm) complexes, the crystal and molecular structures have been determined by X-ray crystallography. These complexes have shown a nearly pure saddled structure in the crystal, which is further confirmed by the normal-coordinate structural decomposition method. The substituent effects on the CH2 proton as well as meso and CH2 carbon shifts are fairly small in the bis(HIm) complexes. Since these complexes adopt the (d(xy))2(d(xz), d(yz))3 ground state as revealed by the electron paramagnetic resonance (EPR) spectra, the unpaired electron in one of the metal dpi orbitals is delocalized to the porphyrin ring by the interactions with the porphyrin 3e(g)-like orbitals. A fairly small substituent effect is understandable because the 3e(g)-like orbitals have zero coefficients at the meso-carbon atoms. In contrast, a sizable substituent effect is observed when the axial HIm is replaced by (t)BuNC. The Hammett plots exhibit a large negative slope, -220 ppm, for the meso-carbon signals as compared with the corresponding value, +5.4 ppm, in the bis(HIm) complexes. Since the bis((t)BuNC) complexes adopt the (d(xz), d(yz))4(d(xy))1 ground state as revealed by the EPR spectra, the result strongly indicates that the half-filled dxy orbital interacts with the specific porphyrin orbitals that have large coefficients on the meso-carbon atoms. Thus, we have concluded that the major metal-porphyrin orbital interaction in low-spin saddle-shaped complexes with the (d(xz), d(yz))4(d(xy))1 ground state should take place between the d(xy) and a(2u)-like orbital rather than between the dxy and a(1u)-like orbital, though the latter interaction is symmetry-allowed in saddled D(2d) complexes. Fairly weak spin delocalization to the meso-carbon atoms in the complexes with electron-withdrawing groups is then ascribed to the decrease in spin population in the d(xy) orbital due to a smaller energy gap between the d(xy) and dpi orbitals. In fact, the energy levels of the d(xy) and dpi orbitals are completely reversed in the complex carrying a strongly electron-withdrawing substituent, the 3,5-bis(trifluoromethyl)phenyl group, which results in the formation of the low-spin complex with an unprecedented (d(xy))2(d(xz), d(yz))3 ground state despite the coordination of (t)BuNC.

On the performance of graphitized meso carbon microbeads (MCMB)–meso carbon fibers (MCF) and synthetic graphite electrodes at elevated temperatures

The behavior of graphite electrodes comprising either synthetic flakes or round-shaped particles, meso carbon microbeads (MCMB) and meso carbon fibers (MCF), were studied at elevated temperatures (up to 80 °C) in standard solutions of ethylene carbonate–ethylmethylcarbonate (EC–EMC)/LiPF 6. Electron microscopy, X-ray diffraction (XRD), and Raman spectroscopy were used in conjunction with standard electrochemical techniques, including impedance spectroscopy. While electrodes comprised of synthetic flakes demonstrated impressive stability, even at 80 °C, MCMB–MCF electrodes demonstrated a rapid capacity fading at elevated temperatures. This capacity fading is due to the formation of thick surface films that contain Li carbonate and Li oxalate as part of their components. The thick surface films are formed upon cycling because of the surface properties of round-shaped graphite particles, as discussed herein. The MCMB–MCF electrodes fail at high temperature because of the high impedance developed due to the formation of thick surface films.

The Crystal Structure of Cytochrome P460 ofNitrosomonas europaeaReveals a Novel Cytochrome Fold and Heme−Protein Cross-link,

We have determined the 1.8 A X-ray crystal structure of a monoheme c-type cytochrome, cytochrome P460, from Nitrosomonas europea. The chromophore possesses unusual spectral properties analogous to those of the catalytic heme P460 of hydroxylamine oxidoreductase (HAO), the only known heme in biology to withdraw electrons from an iron-coordinated substrate. The analysis reveals a homodimeric structure and elucidates a new c-type cytochrome fold that is predominantly beta-sheet. In addition to the two cysteine thioether links to the porphyrin typical of c-type hemes, there is a third proteinaceous link involving a conserved lysine. The covalent bond is between the lysine side-chain nitrogen and the 13'-meso carbon of the heme, which, following cross-link formation, is sp3-hybridized, demonstrating the loss of conjugation at this position within the porphyrin. The structure has implications for the analogous tyrosine-heme meso carbon cross-link observed in HAO.

Radical Energies and the Regiochemistry of Addition to Heme Groups. Methylperoxy and Nitrite Radical Additions to the Heme of Horseradish Peroxidase

The heme of hemoproteins, as exemplified by horseradish peroxidase (HRP), can undergo additions at the meso carbons and/or vinyl groups of the electrophilic or radical species generated in the catalytic oxidation of halides, pseudohalides, carboxylic acids, aryl and alkyl hydrazines, and other substrates. The determinants of the regiospecificity of these reactions, however, are unclear. We report here modification of the heme of HRP by autocatalytically generated, low-energy NO2* and CH3OO* radicals. The NO2* radical adds regioselectively to the 4- over the 2-vinyl group but does not add to the meso positions. Reaction of HRP with tert-BuOOH does not lead to heme modification; however, reaction with the F152M mutant, in which the heme vinyls are more sterically accessible, results in conversion of the heme 2-vinyl into a 1-hydroxy-2-(methylperoxy)ethyl group [-CH(OH)CH2OOCH3]. [18O]-labeling studies indicate that the hydroxyl group in this adduct derives from water and the methylperoxide oxygens from O2. Under anaerobic conditions, methyl radicals formed by fragmentation of the autocatalytically generated tert-BuO* radical add to both the delta-meso carbon and the 2-vinyl group. The regiochemistry of these and the other known additions to the heme indicate that only high-energy radicals (e.g., CH3*) add to the meso carbon. Less energetic radicals, including NO2* and CH3OO*, add to heme vinyl groups if they are small enough but do not add to the meso carbons. Electrophilic species such as HOBr, HOCl, and HOSCN add to vinyl groups but do not react with the meso carbons. This meso- versus vinyl-reactivity paradigm, which appears to be general for autocatalytic additions to heme prosthetic groups, suggests that meso hydroxylation of the heme by heme oxygenase occurs by a controlled radical reaction rather than by electrophilic addition.

Safety Performance of Large and High-Power Lithium-Ion Batteries with Manganese Spinel and Meso Carbon Fiber

Three different-sized lithium-ion cells for hybrid electric vehicles nominal capacity 5, 8, and 17 Ah, were fabricated using lithium-rich mangnese spinel Li 1.1 Mn 1.9 O 4 (LM) as a positive active material and meso carbon fiber (MCF) as a negative active material. Overcharge tests at about 5, 16, 100 and 200 A current were carried out to estimate a safety level of LM/MCF cells. As a result of the overcharge test, all cells were not fired and did not burst and themal runaway of the 5 and 17 Ah cells did not occur at 1C rate. LM/MCF cells have great ability for safety under high-rate overcharge. However, thermal runaway occurred at 12C-40C rate overcharge. Thermal runaway depends strongly on the C rate at overcharge.

Chemical and electrochemical oxidation of N-alkyl cyclo[n]pyrroles

Cyclo[n]pyrroles ( n = 6, 7, and 8), are expanded porphyrins that lack bridging meso carbon atoms. They adopt conformations that are near-planar and show features that are consistent with global aromaticity. In previous work, involving studies of cyclo[8]pyrroles, it was found that, in contrast to what is true for porphyrins, reductive per- N -alkylation led to the formation of non-planar products that displayed few signs of extended conjugation. These octa- N -alkylated species could be reoxidized electrochemically to produce dicationic, octa- N -substituted analogues of the starting aromatic cyclo[8]pyrroles. We have now extended this study to cyclo[6]pyrrole, and have found that reductive per- N -methylation can be readily effected using methyl iodide. However, in contrast to what is true in the case of cyclo[8]pyrroles, efforts to obtain the fully N -ethylated or N -benzylated products proved unsuccessful. Moreover, in the case of the hexa- N -methylated cyclo[6]-pyrrole product no viable chemical means of oxidizing it to the putative aromatic dication could be found. However, evidence for the formation of such species was obtained by electrochemical means. The differences between cyclo[6]- and cyclo[8]pyrrole highlight the effect of ring size in mediating the redox and reactivity chemistry within what is otherwise a closely matched pair of porphyrin analogues.

13C NMR Spectroscopy of Core Heme Carbons as a Simple Tool to Elucidate the Coordination State of Ferric High-Spin Heme Proteins

Evidence is presented demonstrating that the magnitudes of the 13C chemical shifts originating from heme meso carbons provide a straightforward diagnostic tool to elucidate the coordination state of high-spin heme proteins and enzymes. Pentacoordinate high-spin heme centers exhibit 13C meso shifts centered at approximately 250 ppm, whereas their hexacoordinate counterparts exhibit 13C shifts centered at approximately -80 ppm. The relatively small spectral window (400 to -100 ppm) covering the meso-13C shifts, the relatively narrow lines of these resonances, and the availability of biosynthetic methods to prepare 13C-labeled heme (Rivera, M.; Walker, F. A. Anal. Biochem. 1995, 230, 295-302) make this approach practical. The theoretical basis for the distinct chemical shifts observed for meso carbons from hexacoordinate high-spin hemes relative to their pentacoordinate counterparts are now well understood (Cheng, R.-J.; Chen, P. Y.; Lovell, T.; Liu, T.; Noodleman, L.; Case, D. A. J. Am. Chem. Soc. 2003, 125, 6774-6783), which indicates that the magnitude of the meso-carbon chemical shifts can be used as a simple and reliable diagnostic tool for determining the coordination state of the heme active sites, independent of the nature of the proximal ligand. Proof of the principle for the 13C NMR spectroscopic approach is demonstrated using hexa- and pentacoordinate myoglobin. Subsequently, 13C NMR spectroscopy has been used to unambiguously determine that a recently discovered heme protein from Shigella dysenteriae (ShuT) is pentacoordinate.

Cadmium(II) and Zinc(II) Complexes ofS-Confused Thiaporphyrin

The synthesis of 5,10,15,20-tetraphenyl-2-thia-21-carbaporphyrin [S-confused thiaporphyrin, (SCPH)H] was optimized. The formation of the phlorin was detected, which was saturated at the meso carbon adjacent to thiophene. Phlorin converted readily to (SCPH)H in the final oxidation process. Insertion of cadmium(II) and zinc(II) into S-confused thiaporphyrin yielded (SCPH)Cd(II)Cl and (SCPH)Zn(II)Cl complexes. The macrocycle acted as a monoanionic ligand. Three nitrogen atoms and the C(21)H fragment of the inverted thiophene occupied equatorial positions. The compensation of the metal charge required the apical chloride coordination. The characteristic C(21)H resonances of the inverted thiophene ring were located at 1.71 and 1.86 ppm in the 1H NMR spectra of (SCPH)Cd(II)Cl and (SCPH)Zn(II)Cl, respectively. The proximity of the thiophene fragment to the metal ion induced direct scalar couplings between the spin-active nucleus of the metal (111/113Cd) and the adjacent 1H nucleus (J(CdH) = 8.97 Hz). The interaction of the metal ion and C(21)H also was reflected by significant changes of C(21) chemical shifts: (SCPH)Zn(II)Cl, 92.9 ppm and (SCPH)Cd(II)Cl, 88.2 ppm (free ligand (SCPH)H, 123.7 ppm). The X-ray analysis performed for (SCPH)Cd(II)Cl confirmed the side-on cadmium-thiophene interaction. The Cd...C(21) distance (2.615(7) A) exceeded the typical Cd-C bond lengths, but was much shorter than the corresponding van der Waals contact. The density functional theory (DFT) was applied to model the molecular structures of zinc(II) and cadmium(II) complexes of S-confused thiaporphyrin. Subsequent AIM analysis demonstrated that the accumulation of electron density between the metal and thiophene, which is necessary to induce these couplings, was fairly small. A bond path linked the cadmium(II) ion to the proximate C(22) carbon of the thiophene.

13C NMR Studies of the Electronic Structure of Low-Spin Iron(III) Tetraphenylchlorin Complexes

A series of low-spin six-coordinate (tetraphenylchlorinato)iron(III) complexes [Fe(TPC)(L)2]+/- (L = 1-MeIm, CN-, 4-CNPy, and (t)BuNC) have been prepared, and their (13)C NMR spectra have been examined to reveal the electronic structure. These complexes exist as the mixture of the two isomers with the (d(xy))2(d(xz), d(yz))3 and (d(xz), d(yz))4(d(xy))1 ground states. Contribution of the (d(xz), d(yz))4(d(xy))1 isomer has increased as the axial ligand changes from 1-MeIm, to CN(-) (in CD2Cl2 solution), CN- (in CD(3)OD solution), and 4-CNPy, and then to tBuNC as revealed by the meso and pyrroline carbon chemical shifts; the meso carbon signals at 146 and -19 ppm in [Fe(TPC)(1-MeIm)2]+ shifted to 763 and 700 ppm in [Fe(TPC)(tBuNC)2]+. In the case of the CN- complex, the population of the (d(xz), d(yz))4(d(xy))1 isomer has increased to a great extent when the solvent is changed from CD2Cl2 to CD3OD. The result is ascribed to the stabilization of the d(xz) and d(yz) orbitals of iron(III) caused by the hydrogen bonding between methanol and the coordinated cyanide ligand. Comparison of the 13C NMR data of the TPC complexes with those of the TPP, OEP, and OEC complexes has revealed that the populations of the (d(xz), d(yz))4(d(xy))1 isomer in TPC complexes are much larger than those in the corresponding TPP, OEC, and OEP complexes carrying the same axial ligands.

Nitric acid promoted formation of an N-confused porphyrin-derived porphodimethene and a violinoid

The nitration of free-base N -confused porphyrin led to a novel 5,10-meso-dihydroxy- N -confused porphodimethene and an open-ring N -confused violinoid. The results support nitration occurring first, followed by nucleophilic addition of a hydroxyl group and a parallel reaction of oxygenolysis to cause the ring-opening. The nitro group substituted at the inner carbon of the inverted pyrrole ring is located on both the porphodimethene and violinoid. In the case of the porphodimethene, two dihydroxyl groups with υ( OH ) at 3404 cm−1 are arranged in a syn conformation at the same side with the nitro group. The violinoid exhibits υ( C = O ) at 1659 cm−1. NMR and structure determination suggest that oxygenolysis occurs selectively at the C=C bond between the α-pyrrole and meso carbon closest to the amino NH of the inverted pyrrole ring. The single crystal structure of porphodimethene gave a 50% disorder between the peripheral nitrogen and carbon atom on the inverted pyrrole ring, while a dimeric structure assembled through hydrogen bonding interactions was observed in the crystal lattice of the violinoid.

Liquid/Liquid Interface Polymerized Porphyrin Membranes Displaying Size-Selective Molecular and Ionic Permeability

Thin polymeric membranes have been formed by liquid/liquid interfacial copolymerization of a sterically demanding tetraphenylporphyrin derivative having reactive phenol substituents and a second porphyrin having reactive acid chloride groups. The out-of-plane steric demand is created by 3,5-hexoxyphenyl groups positioned at two of the four meso carbons of the porphyrin ring. The bulky substituents were designed to create local pockets and extended pores within the resulting ester-linked copolymer. Quantitative measures of molecular and ionic transport were obtained by placing membranes over microelectrodes and recording voltammetric responses from redox-active probes. The membranes were found to be permeable to small molecules and ions, but blocking toward larger ones, displaying a sharp size cutoff at a probe diameter of ca. 3.5 A. Molecular transport can be modulated by axially ligating pore-blocking moieties to available porphyrin metal centers.

Influence of Electrode Active Materials on Safety Performance of Large and High-Power Li-Ion Batteries for Hybrid Electric Vehicles

Large lithium-ion cells with more than 1200 W/kg power were fabricated using Li 1.1 (Ni 0.025 Ti 0.025 )Mn 1.85 O 4 (LM) and LiNi 0.78 Co 0.19 Al 0.03 M x O 2 (M: Na, Sr, Ba, x = 0.0005-0.1) (LN) as a positive active material, and graphitized carbon (KS25) and meso carbon fiber (MCF) as a negative active material. Overcharge tests at 100 A were carried out to estimate a safety level. From the overcharge test, the safety level of the cells are arranged Cell C (LN/MCF) > Cell A(LM/KS25) > Cell B(LN/KS25). Thermal stability of the active materials are arranged LM > LN as positive, and MCF > KS25 as negative from differential thermal analysis of each material with electrolyte. The safety level of the cells can be explained by the thermal stability of the each active material.

Novel Aspects of Corrole Chemistry

Corrole is one of the first examples of porphyrin analogs reported in the literature. This class of compounds has received a great attention, because of their promising exploitation in different fields, ranging from medicine to material chemistry. Among them, corrole can be considered the prototypical example of contracted porphyrins, with one of the meso carbon bridges missing. Although this macrocycle was first reported more than thirty years ago, only recently more attention has been devoted to the chemistry of corrole. The recent availability of efficient and facile syntheses of meso-substituted corroles has probably been the shuttle for the impressive flourishing of corrole-related papers appearing in literature in the last few years. The aim of this review is to highlight the latest reports in the synthetic chemistry of corrole, with special attention to the synthetic strategies and peripheral functionalizations of this macrocycle.

Modified Expanded Corrole–Ferrocene Conjugates: Syntheses, Structure and Properties

Syntheses, characterization and properties of expanded corrole-ferrocene conjugates are reported. Ferrocenyl group are covalently linked to the corrole macrocycle through three different spacers groups. The synthetic strategy involved prior insertion of ferrocene with spacers to the dipyrromethane unit followed by a "3+2" acid-catalyzed oxidative coupling methodology. The optical and emission data of the expanded corrole-ferrocene conjugates depend on the nature and length of the spacer groups and the maximum effects are seen where ferrocene is directly linked to the meso carbon of macrocycle. The single crystal X-ray structure of two expanded corrole-ferrocene conjugates; [22]pentaphyrin (1.1.0.1.0) with different meso substituents, clearly reveal shortening of the C-C bond length linking the meso carbon and the aryl substituent containing the ferrocene moiety relative to meso aryl substituents without ferrocene. The results suggest that an electronic interaction between the two pi systems. Electrochemical data reveal harder oxidation for the ferrocene unit in the conjugates relative to free ferrocene; this suggests the electron donating nature of the ferrocene. The first corrole ring oxidation shows easier oxidation relative to 1 and the magnitude of shifts in potential is inversely proportional to the length of spacer. The molecular first hyperpolarizabilities (beta) measured at 1064 nm by HRS method vary in the range 20-32x10(-30) esu and imply that the beta values can be increased by enhancing the number of mobile electrons in the conjugation. The conjugates form 1:1 metal complex with the Rh(I) where rhodium is coordinated to one amino and one imino nitrogen of the dipyrromethane unit.

Azide-Inhibited Bacterial Heme Oxygenases Exhibit an S = 3/2 (dxz,dyz)3(dxy)1(dz2)1 Spin State: Mechanistic Implications for Heme Oxidation

The azide complexes of heme oxygenase from Pseudomonas aeruginosa (pa-HO) and Neisseriae meningitidis (nm-HO) have been studied with the aid of (1)H and (13)C NMR spectroscopy. These complexes have been shown to exist as an equilibrium mixture of two populations, one exhibiting an S = (1)/(2), (d(xy))(2)(d(xz), d(yz))(3) electron configuration and planar heme and a second with a novel S = (3)/(2), (d(xz), d(yz))(3)(d(xy))(1)(d(z)(2))(1) spin state and nonplanar heme. At physiologically relevant temperatures, the equilibrium shifts in the direction of the population exhibiting the latter electron configuration and nonplanar heme, whereas at temperatures approaching the freezing point of water, the equilibrium shifts in the direction of the population with the former electronic structure and planar heme. These findings indicate that the microenvironment of the distal pocket in heme oxygenase is unique among heme-containing proteins in that it lowers the sigma-donating (field strength) ability of the distal ligand and, therefore, promotes the attainment of heme electronic structures thus far only observed in heme oxygenase. When the field strength of the distal ligand is slightly lower than that of azide, such as OH(-) (J. Am. Chem. Soc. 2003, 125, 11842), the corresponding complex exists as a mixture of populations with nonplanar hemes and electronic structures that place significant spin density at the meso positions. The ease with which these unusual heme electronic structures are attained by heme oxygenase is likely related to activation of meso carbon reactivity which, in turn, facilitates hydroxylation of a meso carbon by the obligatory ferric hydroperoxide intermediate.

EPR, ENDOR, and DFT Studies on (β‐Octahalo‐meso‐tetraarylporphyrin)copper Complexes: Characterization of the Metal(d)−Porphyrin(a2u) Orbital Interaction

AbstractA series of planar (porphyrin)copper(II) complexes and their β‐octahalogenated saddled derivatives have been studied by Electron Paramagnetic Resonance (EPR) spectroscopy, Electron Nuclear DOuble Resonance (ENDOR) spectroscopy, and Density Functional Theoretical (DFT) calculations. Both EPR/ENDOR spectroscopy and DFT calculations indicate a decrease in spin density on the central copper(II) ion and on the nitrogen atoms in the saddled compounds relative to the planar complexes. The EPR/ENDOR measurements show that the hyperfine coupling decreases by 12% on the nitrogen atoms and 9% on the copper ion, in going from planar (5,10,15,20‐tetraphenylporphyrin)copper (Cu[TPP]) to saddled (2,3,7,8,12,13,17,18‐octabromo‐5,10,15,20‐tetraphenylporphyrin)copper (Cu[Br8TPP]). Accordingly, saddling results in a decrease in the spin density on the copper ion and on the nitrogen atoms. DFT calculations on Cu[Br8TPP] yield spin populations of 42.4% on the copper ion, 9.9% on each nitrogen atom and 4.9% on each meso carbon atom, relative to DFT spin populations of 62, 10.2 and 0.3% on the copper ion, each nitrogen and each meso carbon atom, respectively, for porphinecopper (Cu[P]). These calculations further indicate that the decrease in spin density on the copper ion in the saddled complexes results from a saddling‐induced Cu(d)−porphyrin(a2u) orbital overlap whereby some of the Cu spin density is delocalized onto the porphyrin ring. The decrease in nitrogen spin population with saddling appears to be a more subtle effect caused by a superposition of two opposing factors. Saddling decreases the overlap between the nitrogen lone pairs and the Cu d orbital on one hand and enhances the overlap between the copper d orbital and the porphyrin a2u HOMO on the other. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing

New redox active molecular macrocyclic architectures characterized by a direct connection between dipyrrin, tripyrrin and ferrocenyl fragments have been synthesized and characterized. Contrarily to fully conjugated porphyrins, in which four pyrrole moieties contribute to the overall aromatic pi-electronic system and behave as a unique electroactive species, calixphyrins can be regarded as an assembly of independent redox active pyrrole and conjugated oligopyrrole fragments linked through sp(3) hybridized meso carbon atoms. The disruption of the conjugation pathway not only multiplies the number of redox centres throughout the molecule but also leads to a large variety of molecular architectures with specific physico-chemical properties. These novel ferrocene containing hybrid macrocycles exhibit especially attractive electronic and structural features suited for use as molecular sensing tools. An efficient voltammetric sensing of exogenic electron rich anionic species could especially be performed using a metallo-calix[4]phyrin-(1.1.1.1) through the displacement of the labile axial binding site, the perturbation of the Fc(0/+) redox couple being directly related to complexed species features.