Search

Three water-soluble quaternized metal-free tetra-(3-pyridyl)bacteriochlorins were synthesized and characterized by UV-vis, MCD, and NMR spectroscopy as well as elemental analysis. DFT calculations are indicative of the [Formula: see text]HOMO [Formula: see text] [Formula: see text]LUMO relationship, which correlates well with the experimentally observed by MCD spectroscopy for all bacteriochlorins “reversed” sign sequence in the Vis-NIR region. TDDFT calculations also correctly predict large splitting between the [Formula: see text] and [Formula: see text] bands as well as splitting of the Soret band observed experimentally in all bacteriochlorins.

An efficient synthetic route for the preparation of benzene or 1,2-naphthalene fused and phenyl substituted metal-free tetraazachlorins with yields up to 40% was developed using In ( III ) as a removable template. New substituted tribenzotetraazachlorins derivatives with tert-butyl and phenylsulfanyl groups in β and α position of fused benzene rings, correspondingly, were synthesized by novel approach and their spectral properties were investigated.

Reaction of tetrachlorophthalonitrile with some C -nucleophiles was studied. Only one chlorine atom was substituted regioselectively in the position 4 of benzene ring with diethyl malonate and malononitrile; no reaction occurred in case of bulkier diethyl ethylmalonate and ethylmalononitrile. In case of dimedone the domino substitution of two chlorine atoms, first with C -nucleophile followed by enolate O -nucleophile led to the mixture of two dibenzofuran derivatives. Remaining chlorine aroms n malonate and dibenzofuran derivatives were substituted with thiols, but in malononitrile derivative high acidity of methine proton led to the formation of stable carbanion under basic conditions that prevents further substitution. Hexadecasubstituted zinc phthalocyanines were synthesized from some new phthalonitriles.

Interaction of isomeric 4-nitro- or 3-nitrophthalonitrile with triethyl phosphonoacetate, diethyl cyanomethylphosphonate or tetraethyl methylenediphosphonate in basic conditions resulted in regioselective C -nucleophilic oxidative substitution of hydrogen ortho-located to nitro group, new phthalonitriles with diethoxyphosphorylmethyl or bis(diethoxyphosphoryl)methyl group were isolated in modest yields. In the same conditions one chlorine atom of tetrachlorophthalonitrile was regioselectively substituted with triethyl phosphonoacetate. In basic conditions, both parent phthalonitriles and corresponding zinc phthalocyanines with ortho-located nitro and diethoxyphosphoryl substituted methyl groups are involved in reversible acid-base interaction accompanied with large bathochromic shift of their long wavelength absorption maxima in visible or NIR region, correspondingly. Formation of tetraazachlorin- and tetraaza(iso)bacteriochlorin-like anions is proposed for explanation of this unprecedent bathochromic shift for phthalocyanines.

A new method of preparation and the properties (solubility, aggregation, spectralluminescent properties, singlet oxygen and photobleaching quantum yields) of non-metal 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine are reported. The influence of ionization state on photophysicochemical properties of this dye is also presented.

Three approaches to the synthesis of reduced derivatives of tetraazaporphine such as tetraazachlorin, tetraazabacteriochlorin, and tetraazaisobacteriochlorin are reviewed. The first synthesis of alkyl-substituted tetraazachlorins was achieved by the catalytic hydrogenation of magnesium complexes of tetraazaporphines. Two other synthesis approaches for reduced tetraazaporphines based on the mixed condensation of the precursors with different hydrogenation levels and β–β addition reactions have been developed in the last decade. The use of tetramethylsuccinonitrile as the saturated component in the mixed condensation with derivatives of aromatic and heteroaromatic dicarboxylic acids enable the synthesis of oxidation-resistant benzo-; 1,2- and 2,3-naphtho-; pyrazino-; 2,3- and 3,4-pyridino-fused tetraazachlorins, tetraazabacteriochlorins, and tetraazaisobacteriochlorins. Fullerene conjugates of reduced tetraazaporphine derivatives were obtained using 1,2-dicyanofullerene as the source of the hydrogenated sites. Tetraazaporphine can act as dienophile in Diels-Alder reaction with dienes of the anthracene and cyclopentadiene series and also as dipolarophile in 1,3-dipolar cycloadditions with azomethine ylides and nitrones. In addition, the effect of the reduction of peripheral double bonds in tetraazaporphine macrocycle alone, and in combination with annelation of benzene or heterocyclic rings on the absorption spectra is discussed.

Several Zn (II) and Al (III) phthalocyanines bearing eight or sixteen positive charges on substituents of different structure have been prepared. Synthesized polycationic phthalocyanines have been studied in aqueous and alcoholic media by UV-vis spectroscopy and tested for their efficacy in singlet oxygen photosensitization. It has been found that a minor structural modification at the periphery of the photosensitizer allows control over its key features such as singlet oxygen generation due to specific intermolecular interactions in solution. The efficacy of polycationic phthalocyanines to sensitize tryptophan photobleaching in aqueous media and inactivation of bacteria in sewage water is also structure-dependent. Among the complexes studied, two dyes - zinc octakis(pyridiniomethyl)- and octakis[ N -(2-hydroxyethyl)- N , N -dimethylammoniomethyl]substituted phthalocyanines - are the best sensitizers and have high potential for photodynamic applications.

The importance of singlet oxygen mechanism in photooxidation of phthalocyanine chromophore has been studied for promising singlet oxygen sensitizers: metal-free tetra-tert-butyl phthalocyanine and its Zn , Mg or Al complexes. It has been found that involvement of singlet oxygen in phthalocyanine photodegradation is dependent on the presence and character of the central metal atom, being the most prominent for the metal-free compound and almost negligible for the Al complex. The interaction of dioxygen with metal centers results in a sharp increase of phthalocyanine photooxidation rate.

The kinetics of the oxidative destruction of cobalt phthalocyanine derivatives in aqueous solutions has been investigated in the concentration interval 10−4–10−5 M as a function of the concentration of alkali and the partial pressure of oxygen in the system. The kinetic equation for the initial solution bleaching rate is obtained. A mechanism of cobalt phthalocyanine destruction involving an intermediate Co (II) → Co (III) oxidation step is suggested.

The use of the Diels–Alder reaction of unsubstituted tetraazaporphine as dienophile with some dienes of the anthracene series for the synthesis of novel substituted tetraazachlorins, tetraazabacteriochlorins and tetraazaisobacteriochlorins is reported. The condensation of tetraazaporphine with anthracene, 9,10-dimethyl- or 2,6-di(tert-butyl)anthracene in boiling chlorobenzene gives novel dibenzobarreleno-substituted tetraazachlorins 3–5 in yields of up to 71%. When AlCl3 was used as catalyst in the reaction of tetraazaporphine with 2,6-di(tert-butyl) anthracene, the corresponding cis- and trans-dibenzobarreleno-substituted tetraazabacteriochlorins 6a and 6b were obtained. The reaction of tetraazaporphine with the more active diene 2,3-benzanthracene at 130°C gives mainly benzonaphtho[2,3-b]barreleno-substituted tetraazachlorin 7, while the same reaction conducted at 220°C led to a mixture of cis- and trans isomers of tetraazabacteriochlorins 8a and 8b and tetraazaisobacteriochlorins 9a and 9b. The products were characterized using elemental analysis data and mass, 1H NMR and visible spectra. The effect of hydrogenation of one or two double bonds of the tetraazaporphine macrocycle on the electronic absorption spectra is discussed.

This is a review of the recent studies done by the authors in the area of catalysis and photocatalysis by phthalocyanines and related compounds. Several examples of catalytic processes are given. Special attention is paid to the design of new types of photocatalytic systems for photodynamic therapy of cancer and to the development of novel catalytic methods of cancer treatment.

Catalytic systems consisting of cobalt phthalocyanine grafted to maleic anhydride-styrene copolymer chemically linked with γ-aminopropylated silochrome have been prepared. In the process of sulfide oxidation with air oxygen the specific catalytic activity of these systems depends strongly on the phthalocyanine concentration in the catalyst. At low phthalocyanine concentrations (below 0.4 × 10−6 mol g−1) the catalytic activity is more than an order of magnitude larger than that of homogeneous catalysts and cobalt phthalocyanine adsorbed on a silochrome surface. The different ways of preparing the catalysts are reflected in the kinetic characteristics of the oxidation process.

The reaction with sodium cyanide of the μ-oxo-bridged complex of tetra-4-tert-butyl-substituted iron phthalocyanine (form ‘690’) and that of the product of its treatment with organic bases such as Py, Im, etc. (form ‘627’) result in the formation of the same ferrous bis-cyanide complex Na2[ PctFeII( CN )2] which can be readily oxidized to the analogous ferric complex Na [ PctFeIII( CN )2]. Form ‘690’ has been oxidized to the corresponding ferric μ-oxo complex (form ‘630’). Data for all μ-oxo-bridged complexes (chemical behavior; electronic, NMR, Mössbauer, X-ray photoelectron and ESR spectra; magnetic susceptibility) are discussed, and based on them, the following structures are proposed: ( HPctFeII)2O (form ‘690’), H2[( LPctFeII)2O ] (form ‘627’) and ( PctFeIII)2O (form ‘630’).