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A series of thiol-derivatized porphyrins and the corresponding cobalt and zinc complexes were synthesized from 5-(p-aminophenyl)-10,15,20-triphenylporphyrin (H₂TPP-NH₂), and 5α,15α-bis(o-aminophenyl)porphyrin (H₂DPE- (NH₂)₂). These derivatized porphyrins have a different number of thiol appendages attached via amide linkages at different locations. The thiol-derivatized porphyrins made from H₂TPP-NH₂, H₂TPP-NHC(O)(CH₂)_nSH (n = 2, 4, 5, 10), have one alkyl-thiol appendage attached to the porphyrin through an amide linkage on the p-aminophenyl position. The derivatives made from H₂DPE-(NH₂)₂ have two alkyl-thiol appendages attached to the porphyrin through amide linkages on the o-aminophenyl positions on the same face of the porphyrin ring. These thiol-derivatized porphyrins are important adsorbates for the preparation of thiol–porphyrin monolayers on gold.

We investigated the utility of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) for analyzing porphyrinic compounds using a variety of different synthetic porphyrins, azaporphyrins, phthalocyanines and multiporphyrin arrays. Comparisons of spectra obtained from these analytes deposited either as neat samples or codeposited with neutral or acidic matrices have been made with the goal of identifying conditions that yield minimal demetalation, transmetalation, adduct formation and fragmentation. It was found that the molecular masses of many porphyrins can be successfully measured from neat sample preparations and do not require a matrix to facilitate desorption and ionization, although the measurement of large multiporphyrin arrays was facilitated by the use of matrices. Demetalation of magnesium porphyrins occurred in the presence of acidic matrices, but not with neutral matrices such as 1,4-benzoquinone. Positive ion spectra were obtained for each compound and negative ion spectra were also collected for the azaporphyrins and phthalocyanines. Examination of selected samples (prepared neat, with 1,4-benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone or α-cyano-4-hydroxycinnamic acid) showed that the dominant process of ionization involved oxidation yielding the radical cation M^+· rather than the protonated molecule [M+H]⁺. MALDI-TOF-MS is shown to be a powerful analytical tool for the characterization of diverse synthetic porphyrinic compounds.

The chemistry of nitric oxide (NO) has taken on new dimensions since the discovery, about a decade ago, of a myriad of biological events that NO participates in. Many of the foundations of metal-NO chemistry were laid out earlier by inorganic chemists and biochemists investigating the structures and electronic properties of the heme-NO moiety or its model compounds. Certainly, the persistent work over the last three decades by chemists working with metal nitrosyls has paid off. Current areas of research in heme-NO chemistry include (i) how the NO group approaches and binds to the metal center (or how it dissociates from the metal center); (ii) the ground state and excited state geometries of the metal-NOfragment; (iii) effects of the trans axial ligands on NO orientation and/or dissociation; and (iv) N-N bond formation from NO molecules catalyzed by heme groups.

A brief review is presented of the status of quantum chemical studies of porphyrins and related molecules.

Recent advances in the electron transfer chemistry of metalloporphyrins and related metal complexes are reviewed briefly by focusing not only on the electron transfer processes but also on the subsequent chemical processes associated with electron transfer processes of metalloporphyrins and related metal complexes with macrocyclic ligands.

Resonance Raman spectroscopy is an ideal tool to investigate the structural properties of chromophores embedded in complex (biological) environments. This holds particularly for metalporphyrins which serve as prosthetic group in various proteins. Resonance Raman dispersion spectroscopy involves the measurement of resonance excitation and depolarization ratios of a large number of Raman lines at various excitation energies covering the spectral region of the chromophore's optical absorption bands. Thus, one obtains resonance excitation profiles and the depolarization ratio dispersion of these bands. While the former contains information about the structure of excited electronic states involved in the Raman scattering process, the latter reflects asymmetric perturbations which lower the porphyrin macrocycle symmetry from ideal D_4h. The article introduces and compares different quantum mechanical approaches designed to quantitatively analyze both resonance excitation and the relationship between symmetry lowering and depolarization ratio dispersion.

We review contributions made towards the elucidation of CO and O₂ binding geometries in respiratory proteins. Nuclear magnetic resonance, infrared spectroscopy, Mössbauer spectroscopy, X-ray crystallography and quantum chemistry have all been used to investigate the Fe–ligand interactions. Early experimental results showed linear correlations between ¹⁷O chemical shifts and the infrared stretching frequency (ν_CO) of the CO ligand in carbonmonoxyheme proteins and between the ¹⁷O chemical shift and the ¹³CO shift. These correlations led to early theoretical investigations of the vibrational frequency of carbon monoxide and of the ¹³C and ¹⁷O NMR chemical shifts in the presence of uniform and non-uniform electric fields. Early success in modeling these spectroscopic observables then led to the use of computational methods, in conjunction with experiment, to evaluate ligand-binding geometries in heme proteins. Density functional theory results are described which predict ⁵⁷Fe chemical shifts and Mössbauer electric field gradient tensors, ¹⁷O NMR isotropic chemical shifts, chemical shift tensors and nuclear quadrupole coupling constants (e²qQ/h) as well as ¹³C isotropic chemical shifts and chemical shift tensors in organometallic clusters, heme model metalloporphyrins and in metalloproteins. A principal result is that CO in most heme proteins has an essentially linear and untilted geometry (τ = 4 °, β = 7 °) which is in extremely good agreement with a recently published X-ray synchrotron structure. CO/O₂ discrimination is thus attributable to polar interactions with the distal histidine residue, rather than major Fe–C–O geometric distortions.

The effects of tetrakis(1-methylpyridinium-4-yl)porphyrinatomercury(II) [Hg(TMPyP)]⁴⁺ (6) along with [Pb(TMPyP)]⁴⁺ (7), [Cd(TMPyP)]⁴⁺ (8), and [H₂(TMPyP)]⁴⁺ (1) (free base porphyrin) on DNA cleavage by Haemophilus aegyptius (HaeIII) have been studied using gel electrophoresis, UV-vis absorption spectroscopy, and circular dichroism (CD) spectroscopy. The gel electrophoresis results indicate that in the absence of 6, HaeIII restriction enzyme could not cleave plasmid DNA at a low concentration of 0.2 units μl^-1 after 1 h incubation at 37 °C. However, DNA cleavage occurred in the presence of 6 at the concentrations of 1.0 × 10^-6 and 1.0 × 10^-7M and 0.2 units μl^-1 of HaeIII under the same conditions. In addition, acceleration of DNA cleavage occurred at a higher concentration of HaeIII (0.4 units μl^-1) in the presence of a wider concentration range of 6 from 1.0 × 10^-5 to 1.0 × 10^-7M. 8, 7, and 1 could not enhance DNA cleavage in the presence of HaeIII (0.2 units μl^-1). However, when the concentration of HaeIII was increased to 0.4 units μl^-1, only 8 inhibited DNA cleavage by HaeIII at higher concentrations (1.0 × 10^-5-10^-6M) whereas 6, 7, and 1 did not. The UV-vis and CD spectroscopic results indicate that these porphyrins interact differently with DNA based on their binding modes. 6 enhanced DNA cleavage due to the synergistic effect of the Hg²⁺ ions and the free base porphyrin 1 that dissociated from the mercury(II) porphyrin complex upon binding to DNA which resulted in the enhanced transformation of the DNA conformation from the original B-form to a Z-like conformation, while 8 inhibited HaeIII activity at higher concentrations and 7 and 1 neither enhanced nor inhibited DNA cleavage. A mechanism for this phenomenon is suggested.

Recent developments in the electrochemistry of metalloporphyrins and metallophthalocyanines are reviewed briefly by focusing on the electroanalytical, electrocatalytic and electrochemical sensor applications.

The main topics in resonance Raman spectroscopy presented at ICPP-2 in Kyoto are briefly discussed. These include: (i) coherent spectroscopy and low frequency vibrations of ligand-photodissociated heme proteins, (ii) vibrational relaxation revealed by time-resolved anti-Stokes Raman spectroscopy, (iii) electron transfer in porphyrin arrays, (iv) vibrational assignments of tetraazaporphyrins and (v) resonance Raman spectra of an NO storing protein, nitrophorin.

Recent advances in the catalytic formation of carbon-carbon bonds by metalloporphyrins are surveyed. New studies on cyclopropanation and olefination reactions are discussed and a new application of metalloporphyrin catalysis, the cyclotrimerization of phenylethynes, is presented.

Ten meso-tetraphenylporphyrin-type heterodimers containing a partly or completely β-brominated subunit were synthesized and characterized by UV-visible spectroscopy, cyclic voltammetry and spectroelectrochemistry, showing the presence of low electronic interactions between the two subunits. The investigated compounds are represented as M[(tripp-tpp(Br₄)]M and M[tripp-tpp(Br₈)]M(M = 2H, Zn, Ni, Co and Cu) where tripp-tpp(Br₄) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,3,12,13-tetrabromoporphyrinyl)]-benzene and tripp-tpp(Br₈) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,3,7,8,12,13,17,18-octabromoporphyrinyl)]-benzene. One of the synthesized dimers, H₂[tripp-tpp(Br₈)]H₂, was characterized by a single-crystal X-ray investigation.

Novel chiral systems for the catalytic asymmetric oxidation and cyclopropanation of olefins based on metalloporphyrins containing iron, ruthenium and manganese, have been recently introduced. High catalyst turnover numbers and sometimes high enantiomeric excess were observed. New catalytic reactions with metalloporphyrins have recently been reported; these are the olefination of aldehydes and cyclotrimerization of terminal alkynes. Dendrimers and polymers containing metalloporphyrins, have also been found to be efficient catalysts for oxidation and carbene transfer.

The synthesis of new lipophilic meso-tetraarylporphyrins bearing cardanol is described; cardanol is both a dangerous pollutant and renewable, widely available, relatively low-cost natural material obtained as a byproduct of the cashew industry for the edible use of cashew kernel. Such compounds exhibited unusual chemical and physico-chemical properties.

Electronic absorption spectra of divalent metal (Ni(II) and Cu(II)) complexes of 2,3,7,8,12,13,17,18-octa(bromo/chloro)-5,10,15,20-tetraphenylporphyrins (MOXTPP; X = Br, Cl) were examined in various solvents. M(II) perhaloporphyrins exhibited dramatic shifts in their optical absorption spectral features relative to the corresponding metallotetraphenylporphyrins, MTPPs. Copper(II) perhaloporphyrins show significant red-shifts of the absorption bands in coordinating solvents relative to that observed for nickel(II) perhaloporphyrins. The large red-shift of the electronic absorption bands and the gain in intensity of the longest wavelength band (Q(0,0)), of Cu(II) perhaloporphyrins in certain coordinating solvents is comparable to that found in meso-tetraphenylporphinatozinc(II), ZnTPP. The solvent dependent spectral features of M(II) perhaloporphyrins are attributed to a coordinative interaction of the solvent with the core metal ion induced by the electron deficient porphyrin macrocycle.

A family of meta octa-substituted 5,10,15,20-tetraphenylporphyrin derivatives and their metal (Cu(II) and Zn(II)) complexes were examined by electrochemical studies. These functionalized MTPPs exhibited a dramatic anodic shift (>200 mV) in their first ring redox potentials relative to the para-phenyl substituted-MTPP(X) complexes and follow a fairly linear relationship with the Hammett parameter of the substituents. The extent of Lewis acidity of the core Zn(II) center in these porphyrins was probed by axial ligation of bases of varying pK_a values. The increase in K_eq values of the electron deficient Zn(II) porphyrins are as high as an order of magnitude and increase with anodic shift of the electrochemical redox potentials of the porphyrin. A crystal structure of the Zn(II) octa(carboxyethylester phenyl)porphyrin shows six-coordination geometry with the coordination through peripheral ester groups to form a supramolecular two-dimensional layer structure while the ZnT(3',5'-DMP)P complex exhibited a five-coordinate structure.

Liquid phase catalytic selective hydroxylation of phenol to catechol and hydroquinone was carried out in the presence of metalloporphyrins using hydrogen peroxide as oxidant and water as solvent. Five kinds of metal tetra(p-chlorophenyl)porphrin (T(p-Cl)PPMCl, M = Fe, Co, Mn, Cu, Zn) were studied. It was found that T(p-Cl)PPFeCl had high catalytic activity and diphenol selectivity for the hydroxylation of phenol to catechol and hydroquinone. The influence of various reaction parameters, namely, reaction temperature, solvent, ratio of substrate and oxidant, substrate concentration, the amount of catalyst, reaction time and pH value were investigated systematically. When water was used as solvent (10 mL), the optimum conditions were following: pH = 7, the concentration of phenol was 0.3 g/mL, the molar ratio of phenol and H₂O₂ was 1/2, the molar ratio of catalyst and phenol was 7/100000, the reaction temperature was 65°C and the reaction time was 1.5 h. Under above optimum conditions, the phenol conversion was up to 55.1%, and the selectivity of diphenol was almost up to 99.9%, the molar turnover numbers of the catalyst was about 7500. A possible mechanism was also proposed.

This paper deals with the synthesis of a new hybrid meso-tetraarylporphyrin-cardanol with the cardanol bearing an unsaturated chain. Cardanol is a renewable, natural, widely available and relatively low-cost material obtained as a by-product of the cashew industry which provides cashew kernels for edible use. The unsaturation in the chain in the new hybrid meso-tetraarylporphyrin-cardanol leads to chemical and physico-chemical properties which are different from the saturated derivatives. The unsaturation also allows preparation of the corresponding epoxy compounds as well as self-metathesis derivatives.

The effective 'one-pot' microwave-assisted synthesis of several substituted 5,10,15,20-tetraarylporphyrins is reported. The microwave-assisted insertion of five different transition metals into the 5,10,15,20-tetraphenylporphyrin, 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin and 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin core was also achieved with high yields. In addition to their simplicity, both these straightforward, experimental protocols were also characterized by extremely short reaction times and quite small quantities of solvents employed.

A systematic study on the effect of a catalyst on the aerobic oxidation of cyclohexane was carried out using cobalt isooctanoate, metalloporphyrin p-ClTPPCo and [p-ClTPPFe]₂O as catalysts. The results showed that the metalloporphyrin-catalyzed system performed better than the traditional cobalt salt (Co isooctanoate) in terms of both the reaction conversion and the selectivity of cyclohexanol and cyclohexanone (KA oil). More importantly, we discovered that bisironporphyrin complex, which was traditionally considered to be either non-active or not-so-active for hydrocarbon oxidation, excelled at 155°C, achieving high selectivity for KA oil (80%) and good reaction conversion (13.8%). This result is in sharp contrast to earlier results by others. Meanwhile, the production of adipic acid was also increased and good selectivity of adipic acid among the by-products was also obtained. Our study suggested that [p-ClTPPFe]₂O catalyzed aerobic oxidation could be used to produce adipic acid in addition to KA oil. Some mechanistic rationales were proposed to explain the superior performance of the [p-ClTPPFe]₂O catalyst based on its unique structural and chemical properties.