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CONTENTS

The aromatic character of porphyrinoid systems is commonly attributed to the presence of 18π electron substructures, although this viewpoint has been disputed. Using results from the author's own studies, the bridged [18]annulene model is shown to be a self-consistent and insightful approach for considering the aromatic properties of porphyrin analogs, including carbaporphyrins, tropiporphyrins, azuliporphyrins, N-confused porphyrins, pyrazoloporphyrins, dicarbaporphyrins and dideazaporphyrins.

H₂(TF₅PP) and its metal complexes react with a range of nucleophiles (amines, alcohols, thiols, nitrogen heterocycles, and others) leading to a diversity of porphyrinic materials useful for many applications.

This review of the application of the MCD spectroscopic technique to porphyrinoids and heme binding proteins aims to illustrate the features and unique information that can be obtained and used in the assignment of the optical absorption spectrum, electronic structures of porphyrins and phthalocyanines, and ligand elucidation in heme binding proteins.

The synthetic and photophysical aspects of trimeric systems used as models for various natural components in photosystems constructed with a cofacial bisporphyrin and of another porphyrin attached as a side arm are reviewed. The first series discussed is the case where the three chromophores are different, called donor 1–donor 2–acceptor, specifically where the cofacial fragment is composed of donor 1 and donor 2, and the side arm is the energy acceptor. The second series describes homo-bisporphyrines flanked by another porphyrin as a side arm.

New porphyrin-appended phosphapalladacycles, prepared from the corresponding meso-phosphanylporphyrins and a palladium(II) salt, behaved as precatalysts for a high-temperature Heck reaction between p-bromobenzaldehyde and n-butyl acrylate. The Ni-porphyrin-appended phosphapalladacycle showed considerably higher catalytic efficiency, as well as thermal durability than did the Zn-porphyrin-appended analog.

A complete series of calix[4]arene-substituted porphyrins has been prepared and detailed conformational analysis based on variable-temperature ¹H NMR experiments revealed dynamic phenomena arising from the restricted rotation around the calix[4]arene-porphyrin bond.

The synthesis of a family rigid tris-porphyrins bearing di-ethynyl-anthracenic spacers in which porphyrins are held in a cofacial orientation by an anthracenic spacer is described here, as well as the NMR comparison between the different porphyrinic wires. This constitutes a first step toward the elaboration of more sophisticated light collecting devices. More specifically, these trimers, in which the porphyrins are held in a parallal conformation, constitute an approach toward the synthesis of rigid molecular wires.

The electrochemical and spectroelectrochemical behavior of two planar binuclear naphthalocyanines containing benzene and naphthalene π-conjugated bridges was investigated. The complexes had a tendency to "chemical aging" in the presence of oxygen and light with the formation of a cation radical with low intensity Q-bands. Electrochemical reduction disclosed true optical characteristics of the complexes synthesized.

In this study, it is shown that the introduction of thiazolyl groups in porphyrins boosts their ability to photosensitize the production of singlet oxygen.

The simple dipping of a glass slip into a solution of chiral porphyrin aggregates results in the achievement of solid substrates covered by chiral porphyrin layers.

The absorption spectra of subporphyrazines and subphthalocyanines have been analyzed through the use of TD–DFT calculations. Moving from the SubPz to the SubPc there is a red-shift of both the Q-band and the B-band, although the effect is larger for the former, mainly due to the increase of the HOMO–LUMO energy gap for the triisoindole macrocycle, with respect to the tripyrrole derivative. Supplementary Material

The synthesis, structural and electronic characterization of novel electroactive systems based in porphyrin-fullerene in which the chromophores are linked by an ethynylfluorene spacer unit is reported. Sonogashira couplings have been used in short and efficient sequences to give access to these new molecules on a practical scale. The absorption stu dies, voltamperometric measurements and theoretical calculations at DFT level reveal the push-pull behavior for these systems.

This paper presents the study of the effects of CdTe–TGA quantum dots on optical limiting ability of different phthalocyanine complexes containing Zn, Ga and In central metals, and substituted with benzyloxyphenoxy, phenoxy, tert-butylphenoxy and amino groups in peripheral, non-peripheral, tetra and octa substitution.

This work manifests supramolecular chirality in crystalline assembly of tribromo-monopyridyl-porphyrin induced by inter-porphyrin Br⋯N halogen bonds.

Organic nanoparticles of Mn(III)TPPF₂₀ activate O₂ to catalytically oxidize the allylic positions of cyclohexene to form the alcohol and the ketone in the presense of isobutyraldehyde. Supplementary Material

Two meso-phenyl chloro-substituted copper corroles were synthesized and their electrochemical and spectroelectrochemical properties were characterized. UV-vis and ESR spectra revealed that the electronic ground states of the compounds are solvent dependent. Supplementary Material

The synthesis, spectral and electrochemical properties of β-pyrrole brominated metallocorroles are described, with emphasis on their visible spectra, redox potentials, and HOMO–LUMO gap energies in comparison with β-pyrrole brominated metalloporphyrins.

The parent compound of the trithiadodecaazahexaphyrins has been prepared for the first time. Its thermal stability has been found to be the highest reported to date among the porphyrinoid family.

Multiple photosynthetic reaction centers have successfully been constructed using a supramolecular complex of zinc porphyrin dendrimer with pyridylnaphthalenediimide. Efficient energy migration occurs between the porphyrin units of the dendrimer prior to the electron transfer from the singlet excited state of zinc porphyrin to PyNIm. The lifetime of charge-separated state of in the supramolecular complex of D(ZnP)₁₆ with PyNIm was determined to be 0.83 ms at 298 K.

Protonation of meso-nitrogen atoms and coordination of additional halide ions by haloindium(III) complexes of octaphenylporphyrazine have been studied spectrophotometrically. Coordination of additional F^-, Cl^- or Br^- ions in acid medium leads to rapid demetalation, and in the presence of iodide a peculiar process of the macrocycle reduction also occurs. Supplementary Material

Compared to BPD dimethyl ester or its 8-(1'-hexyloxy) ethyl derivative, the corresponding In(III) analogs produced enhanced PDT efficacy. However, introducing the hexyl ether group or insertion of indium in these molecules did not make any difference in intracellular localization, and all the analogs showed preferential localization in mitochondria. Supplementary Material

A novel and facile approach to porphyrin tweezer scaffolds through copper catalyzed azide alkyne cycloaddition is described. Asymmetric structures that are highly versatile precursors for molecular design arise. The synthesis and characterization by means of photophysical and electrochemical methods and first results on the formation of dye-sensitized solar cells (DSSC) are described.

Novel 18π octaisopropyltetraphenylporphyrin (OiPTPPH₂) was prepared from 3,4-diisopropylpyrrole. Oxidation of this highly sterically hindered porphyrin furnished novel metal-free 16π OiPTPP, which is the most distorted 16π porphyrin to date and is more stable than previously isolated metal-free 16π porphyrins. Supplementary Material

The Soret maxima of a number of metallotriarylcorroles shift sensitively in response to varying substituents on the meso-aryl groups. The effect is most pronounced for Cu corroles and has been attributed to a small HOMO–LUMO gap. CrO corroles share a small HOMO–LUMO gap with Cu corroles, as well as a substantially metal-based LUMO, yet the Soret maxima of CrO triarylcorroles do not shift in response to substitution on the meso-aryl groups. MoO corroles are substituent-insensitive in the same sense. Supplementary Material

Electrochemical and photochemical studies on the water-soluble tin(IV) porphyrin 1 suggests that it forms a phlorin species and hence that a π-radical anion mechanism is not likely to explain the photocatalytic ability of this and other related tin(IV) porphyrins. Supplementary Material