CONTENTS

General strategies for the preparation of peripherally substituted phthalocyanines, naphthalocyanines, anthracyanines, aza-analogs of phthalocyanines, and tetraazaporphyrins have been discussed. An influence of the types and positions of the substituents attached to the macrocyclic core on the optical properties of these compounds has been generalized. In many cases, poorly known methodologies, published in mostly unavailable Russian journals, were highlighted throughout this review.

The synthesis of new binuclear rhodium(III) and iridium(III) semi-sandwich complexes of a Schiff-base expanded porphyrin is reported here. Single crystal X-ray diffraction analyses and complementary NMR studies provide evidence for the existence of strong intramolecular hydrogen-bonding interactions between the pyrrolic NH protons and the chloride ligand both in dichloromethane solution and in the solid state. Supplementary Material

The target compounds were synthesized: 15 phthalocyanines from 2, 3-dicyanohydroquinone in 3 steps via 1,2-dicyanobenzene-3,6-bis-(trifluorate) and 1,2-dicyanobenzene-3,6-thiophenols. The Q bands of obtained compounds appeared in the near-infrared region. In particular, 1,4,8,11,15,18,22,25-octakis(thiophenylmethyl)phthalocyaninate lead shows a Q band at 857 nm. Furthermore, non-colored transparent films in the visible region can be produced.

This review focuses on the photophysical processes and dynamics in the light harvesting devices, notably LH II, in the heavily investigated purple photosynthetic bacteria, and compares these parameters with our cofacial bisporphyrin dyads build upon octa-etio-porphyrin chromophores and rigid and semi-rigid spacers.

δ-(dihydroxo)dipalladium(II) complex with N²¹, N²²-etheno bridged tetraphenylporphyrin ligand was employed in the catalytic photooxidation of phenol derivatives in aerated homogeneous solution with visible light irradiation. The Pd complex promoted degradation of p-tert-butylphenol and selective photooxidation of some phenol derivatives to afford the corresponding quinones. This Pd complex showed higher light durability compared with ordinary porphyrin free base and its Pd complex.

The tetrasulfonated Cu^II(tspc)^4-, tspc = 4,4‣,4″,4‴-phthalocyaninetetrasulfonate, and the trisulfonated Co^II(trspc)^3-, trspc = n,n‣,n″-phthalocyanine- trisulfonate where n, n‣ and n″ indicate the sulfonated positions of the various isomers, were covalently linked to a poly(ethyleneimine). The redox reactions of the phthalocyanine pendants with pulse radiolytically generated radicals (e^-_sol, C^∙H₂OH, (CH₃)₂COHC^∙H₂, CO₂^∙-, N₃^∙ and SO₄^∙-) produce phthalocyanine radicals, Cu(I) and Co^III-hydroxyalkyl reaction intermediates. Supplementary Material

Self-assembled monolayer (SAM) films of purposely synthesized zinc and magnesium diporphyrin derivatives, 1b and 1c, have been deposited on the surface of gold-coated glass substrates. The SAM films were characterized by RAIR and fluorescence spectroscopy. The potential for the films to promote the oxidation of tryptophan within human serum albumin upon irradiation with white light has been demonstrated and attributed to the porphyrins acting as photosensitizers of oxygen to form oxidizing species.

An efficient stereocontrolled synthesis of an A-B-C-tricycle fragment for a structural model of tolyporphin is described. One of the two key steps is a selective ring-opening reaction of the lactone cycle which introduces the chirality into synthetic compounds. The other key step is the combination of A ring with B-C-bicycle via a two-time Eschenmoser sulfide contraction.

A novel cobalt(II) porphyrin lipoic acid derivative was synthesized starting from deuteroporphyrin(IX)bis-alcohol and enantiomerically enriched lipoic acid. The two disulfide functionalities of the lipoic acid moieties allowed its immobilization on gold by a self-assembly method. It was found that the Co(II) porphyrin self-assembled monolayer is electroactive and exhibits catalytic activity towards reduction of oxygen.

Three novel tetrathiafulvalene-annulated metalloporphyrazines with electron-withdrawing pentoxycarbonyl groups at the periphery were synthesized via the cyclotetramerization of dipentyl 6,7-dicyanotetrathiafulvalen-2,3-dicarboxylate in the presence of corresponding metal salts (Zn(OAc)₂·2H₂O, Cu(OAc)₂·2H₂O and NiCl₂) and in pentanol. Solution electrochemical data showed one reductive and three oxidative processes within a -2000 mV to +2200 mV potential window. Supplementary Material

We report syntheses, molecular structures and magnetic susceptibilities of three meso-substituted high-spin iron(III) porphyrinate complexes ([Fe(TEtP)(Cl)], [Fe(TPrP)(Cl)], and [Fe(THexP)(Cl)]). It was determined that the inter-ring interactions within each dimeric unit change upon alteration of the alkyl groups at the meso positions. Magnetic exchange couplings between iron centers of the dimers are in accord with the trends in structural inter-ring geometries.