Investigation of Structural and Optical Properties of Some [1,4]Dithiine-porphyrazine Dyes

1,4-Bis(p-tolylamino)-6,7-dichloroanthraquinone 1 when reacted with di(sodiothio)-maleonitrile 2 afforded heterocyclic thianone compound, 5,12-dioxo-5,12-dihydroanthro[2,3-b][1,4]dithiine-2,3-dicarbonitrile 3. Using lithium/pentanol and acetic acid, the dicarbonitrile product 3 was cyclotetramerized, yielding the matching tetra 5,12-dioxo-5,12-dihydroanthro[2,3-b][1,4]dithiine-porphyrazine dye compound (2H-Pz) 4a. The dicarbonitrile molecule was a ring-shaped metallic product utilizing metallic salt and quinoline, yielding the corresponding tetra 5,12-dioxo-5,12-dihydroanthro[2,3-b][1,4]dithiine-porphyrazinato-metal II dyes (M-Pz), M = Zn, Co, or Ni 4b–d. The produced compounds’ elemental analysis investigation, Infrared, and nuclear magnetic resonance spectrum information accord with the structures attributed to them. The cyclotetramerization and complexation reactions are ensured by the molecular weight and metal load of the produced products. The inclusion of electron-donating groups resulted in a lower optical band gap of the produced dye sensitizers, with “push–pull” promotion of about 1.55 eV. The prepared substituted porphyrazines reveal high absorption in the UV–VIS region, which could be of potential value as a building block for novel electronic and optical materials as well as a sensor for technology. This is considered for improving solar cell absorption. The absorption bands of the synthesized porphyrazine dyes extend beyond 800 nm, so these dyes could be useful in various optoelectronic applications.     

Kinetic characteristics of the destruction of β,β-annelated porphyrazines in a nitrogen-containing base–dimethylsulfoxide system

The state of tetra(1,2,5-thiadiazolo)porphyrazine in a dimethyl sulfoxide medium is investigated. Relatively high stability is observed for the resulting proton-transfer complex, and a chemical structure is proposed for it. It is shown that the nature of the substituent in the porphyrazine macrocycle influences the kinetic parameters of the destruction of tetra(1,2,5-thiadiazolo)porphyrazine, tetra(5-tert-butylpyrazino) porphyrazine, octaethyltetrapyrazinoporphyrazine, and octaphenyltetrapyrazinoporphyrazine in a nitrogen-containing base–dimethylsulfoxide system. The effect the NH acidity of the porphyrazine macrocycle and the nature of the nitrogenous bases have on the reaction rate and activation parameters of the destruction of β,β-annelated porphyrazine proton-transfer complexes is established.     

Acid-base properties of thianaphthene-annulated porphyrazine and tetra(pyrazino)porphyrazine complexes with aluminum group metals

Acid-base properties of Al(III), Ga(III), and In(III) complexes with tert-butyl-substituted thianaphthene-annulated porphyrazine and tetra(2,3-pyrazino)porphyrazine in proton-donor medium (CH₂Cl₂-CF₃COOH) were studied by spectrophotometric titration. The concentration stability constants of the singly protonated complexes were determined. The effects of the metal nature and aromatic heterocyclic fragment on the basicity of meso-nitrogen atoms were analyzed. Negative inductive effect of the sulfur atom in the thianaphthene fragment reduces the basicity of the meso-nitrogen atoms as compared to analogous porphyrazine and phthalocyanine complexes. Acid-base transformations of the thianaphthene-annulated tetra(2,3-pyrazino)porphyrazine involve both meso-nitrogen atoms and those in the pyrazine rings.     

Kinetic stability of substituted tetrapyrazinoporphyrazines in a system nitrogen base-dimethylsulfoxide

The state of tetra(5-tert-butylpyrazino)porphyrazine, octaethyltetrapyrazinoporphyrazine, octaphenyltetrapyrazinoporphyrazine in DMSO medium was studied. It was found that the complexes formed with the proton transfer exhibit a relatively high stability. In strong basic media these complexes are kinetically unstable. The influence of the nature of cyclic and acyclic nitrogen-containing bases, as well as the influence of NH-acidity of the porphyrazine macrocycle on the rate and activation parameters of decomposition of the proton-transfer complexes of tetra(5-tert-butylpyrazino)porphyrazine, octaethyltetrapyrazinoporphyrazine, and octaphenyltetrapyrazinoporphyrazine was established.     

Metal complexes of tetra(6-tert-butyl-2,3-quinolino)porphyrazine: I. Synthesis

Complexes of tetra(6-tert-butyl-2,3-quinolino)porphyrazine with Cu, Co, Zn, and Ni soluble in hydrophobic liquids were synthesized for the first time by template tetramerization of derivatives of 6-tert-butylquinoline-2,3-dicarboxylic acid formed from the corresponding acid in the course of carbamide synthesis in presence of the bivalent metal ions.     

Nitro-substituted porphyrazines

This nitration of tetra (tert-butyl)porphyrazine and its metal complexes with different nitrating agents has given their mono-, di-, tri-, and tetra-nistro-derivatives; the metal complexes have also been obtained by the metallation of the corresponding metal—free nitroporphyrazines. The structure of the synthesized compounds has been confirmed by electron and mass spectra, and by PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 30–35, January, 1994.     

Synthesis of Biphenols Containing Anhydride,Imido, or Dicyano Arylene Moieties

The novel biphenols, 3,6-bis(4-hydroxyphenyl)phthalic anhydride (2) and 3,6-bis(4-hydroxyphenyl)benzene-1,2-dicarbonitrile (15) were synthesized. Reaction of trans-anethole (4-propenylanisole) (6) with the Schiff base 7 yielded l,4-bis((4-methoxyphenyl)-l,3-butadiene (8). Diels-Alder reactions with maleic anhydride or fumaronitrile followed by dehydrogenation and demethylation gave the corresponding biphenols in good yields (ca. 73%). Reaction of 2 with primary amines yields the corresponding imides.     

Synthesis, acid-base properties, and deselenation of 5,6,8,9,11,12-hexakis(4-tert-butylphenyl)[1,2,5]selenadiazolo[3,4-b]porphyrazine

Cross cyclotetramerization of bis(4-tert-butylphenyl)fumaronitrile with 1,2,5-selenadiazole-3,4-dicarbonitrile in the presence of magnesium butoxide as template afforded a mixture of magnesium(II) porphyrazine complexes, from which magnesium complex of 5,6,8,9,11,12-hexakis(4-tert-butylphenyl)[1,2,5]selenadiazolo[3,4-b]porphyrazine was isolated by column chromatography and was subjected to demetalation on treatment with trifluoroacetic acid. The free ligand was found to undergo protonation at one meso-nitrogen atom in acid medium and deprotonation of one pyrrole ring to form monoanion by the action of bases. Reductive deselenation of the title compound with formation of vicinal diamino porphyrazine was studied by spectral and kinetic methods, and a mechanism involving two hydrosulfide ions was proposed.     

Synthesis,X-ray crystal structure,UV/visible linear and nonlinear (optical limiting) spectral properties of symmetrical and unsymmetrical porphyrazines with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene moieties

Co-cyclization of 1,2,5-thiadiazole-3,4-dicarbonitrile and 3,6-diamyloxyphthalodinitrile in the presence of magnesium or lithium amylate in amyl alcohol leads to mixtures containing the Mg derivatives of the symmetrical species tetrakis(1,2,5-thiadiazolo)porphyrazine, (S(4))PzH(2), and tetrakis(1,4-diamyloxybenzo)porphyrazine, (A(4))PzH(2), and the low-symmetry macrocycles bearing peripheral 1,2,5-thiadiazole and 1,4-diamyloxybenzene rings in the ratio 1:3, 2:2 (cis and trans), and 3:1, that is, (SA(3))PzH(2), (S(2)A(2))PzH(2), (SASA)PzH(2), and (S(3)A)PzH(2), respectively. The basic Mg materials were converted to the corresponding free-base macrocycles by treatment with CF(3)COOH. The species were separated from the mixtures by chromatography, either as Mg complexes or demetalated materials. With results on (S(4))PzH(2) and (SA(3))PzH(2) in hand, including crystallographic work on the latter, a general chemical physical investigation has been carried out of all the symmetrical and unsymmetrical free-base macrocycles. The structures of the species (S(2)A(2))PzH(2) and (A(4))PzH(2). were elucidated by single-crystal X-ray crystallography. The effect of the progressive variation of the macrocyclic structure along the series, from the symmetrical (S(4))PzH(2) to its symmetrical partner (A(4))PzH(2) via the low-symmetry 3:1, 2:2 (cis and trans), and 1:3 macrocycles, was studied by IR, (1)H NMR, and UV/Vis linear and nonlinear (optical limiting) measurements. The results are interpreted on the basis of intra- and intermolecular interactions between the electron-deficient 1,2,5-thiadiazole and the electron-donating 1,4-diamyloxybenzene moieties.     

Reaction of 5-(3,4-dimethoxyphenyl)pyrazine-2,3-dicarbonitrile with alkyl radicals

The reaction of 5-(3,4-dimethoxyphenyl)pyrazine-2,3-dicarbonitrile (Ib) with alkyl radicals gives addition products at the C(6)-position of the pyrazine ring as the intermediates which collapse into substitution products, 6-alkyl-5-(3,4-dimethoxyphenylpyrazine-2,3-dicarbonitrile (II), under oxidative conditions. Under non-oxidative conditions the intermediate is converted into dihydropyrazine derivatives, 6-alkyl-(3,4-dimethoxy-phenyl)-5,6-dihydropyrazine-2,3-dicarbonitrile (III), and 3,6-disubstituted pyrazine derivatives, 3,6-dialkyl-5-(3,4-dimethoxyphenyl)pyrazine-2-carbonitrile (IV) and 3-acyl-6-alkyl-5-(3,4-dimethoxyphenyl)pyrazine-2-carbonitrile (V).     

Synthesis and spectral parameters of tetra(6-<Emphasis Type="Italic">tert</Emphasis>-butyl-2,3-quinoxalino)porphyrazine and its metal complexes

Tetra(6-tert-butyl-2,3-quinoxalino)porphyrazine and its complexes with bivalent metals were synthesized for the first time by template tetramerization of 6-tert-butylquinoxaline-2,3-dicarbonitrile. The obtained macrocyclic compounds are soluble in hydrophobic solvents. Their electronic absorption spectra in organic solvents and the spectra of the corresponding protonated forms in sulfuric acid were studied.     

Synthesis of mono- and disubstituted tetra(tert-butyl)porphyrazines

Bromination of tetra(tert-butyl)porphyrazine by N-bromosuccinimide in chloroform results in the formation of mono- and dibromides, substitution for the bromine atoms of which produced the corresponding cyano, phenoxy, phenylthio, styryl, phenylethynyl and piperidino derivatives. From the monobromide and 2,2-bis(p-hydroxyphenyl)propane, the dimeric porphyrazine 2,2-bis[p-tetra(tert-butyl)porphyrazyloxyphenyl]propane was similarly obtained.Scientific Research Institute of Organic Intermediate Products and Dyes, Moscow 103787. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1206–1212, September, 1994. Original article submitted September 6, 1994.     

Préparation de dithiényl-2-éthène-1,2, de dithiényl-2-pyrimidine-2,4 et de dithiényl-2-pyridazine-3,6

The condensation of 2-thienylmagnesium bromide with (Z)-1,2-dichloroethene 2,4-dichloropyrimidne, 3,6-dichloropyridazine and with a transition metal catalyst is described. The yields of these reactions are very good; 1,2-bis(2-thienyl)ethene and two new heterocyclic compounds 2,4-bis92-thientyl)pyrimidine and 3,6-bis(2-thienyl)pyridazine were obtained in one step from commercial products.     

Radial tetra(ferrocenyl)- and tetra(cymantrenyl)cyclobutadienecobalt complexes: Synthesis and structures

Novel radial tetra(ferrocenyl)- and tetra(cymantrenyl)cyclobutadienecobalt complexes were prepared by metal carbonyls free protocol of [2 + 2] cycloaddition reaction of 1,2-diferrocenyl- or 1,2-dicymantrenylethynes with chlorotris(triphenylphospine)cobalt(I) and carboethoxycyclopentadienide sodium with good yields. The molecular structure of these products was confirmed with X-ray analysis, and their electrochemical behavior was studied.     

Identification of randomers of tetra(tert-butyl)porphyrazine

Randomers of tetra(tert-butyl)porphyrazine, the assignment of which was made on the basis of data from mass spectrometry and high-resolution PMR spectroscopy, were isolated by high-performance liquid column chromatography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1261–1263, September, 1988.     

Kinetic stability of tetra(1,2,5-thiadiazolo)porphyrazine in the system nitrogen-containing base-dimethyl sulfoxide

The behavior of tetra(1,2,5-thiadiazolo)porphyrazine in dimethyl sulfoxide has been studied, and fairly high stability of the resulting proton-transfer complex has been revealed. The complex is kinetically unstable in strongly basic media. The effects of the nitrogen-containing base and NH acidity of the porphyrazine macrocycle on the rate and activation parameters of decomposition of the proton-transfer complex have been estimated.     

Spectral properties and solubility of the lanthanide complexes with substituted and annelated porphyrazines

An analysis of the electronic optical properties and solubility in chloroform and DMF of the erbium and ytterbium complexes with porphyrazine and its octaphenyl- and octa(p-alkylsulfamoylphenyl)-substituted derivatives and tetrapyrazinoporphyrazine and its octaethyl-, tetra(tert-butyl)-, and octaphenyl-substituted derivatives is presented. The dependence of the electronic optical properties and solubility on the composition of the macrocycle of the studied complexes, namely, on the nature of the extraligand and peripheral environment of the porphyrazine macrocycle, is shown.     

Palladium Complex of Camphor-Substituted Tetrapyrazinoporphyrazine as a Stationary Phase of Gas Chromatography

Russian Journal of General Chemistry - Surface modification of the diatomite adsorbent Hezasorb AW-HMDS by tetra(1,7,7-trimethylbicyclo[2.2.1]heptane[2,3-b]pyrazino)porphyrazine Pd(II) was...     

Synthesis and Acid–Base,Absorption, and Fluorescence Properties of Phthalocyanine Derivatives

Russian Journal of General Chemistry - Tetrakis{5,6-bis(4-tert-butylphenyl)pyrazino[2,3-c]}porphyrazine and tetra(4-tert-butyl)phthalocyanine have been synthesized, and their acid–base...     

Kinetic Stability of Tetra(1,2,5-selenodiazolo)porphyrazine in the Nitrogen-Containing Base-Dimethyl Sulfoxide System

Russian Journal of General Chemistry - The behavior of tetra(1,2,5-selenodiazolo)porphyrazine in DMSO and in the DMSO-base (pyridine, 2-methyl-pyridine, morpholine, and piperidine) systems has been...