Synthesis and antimycotic activity of new unsymmetrical substituted zinc phthalocyanines

The synthesis of new unsymmetrical substituted zinc phthalocyanines derivatives has been described; moreover the photodynamic activity of some compounds tested against Candida albicans has been reported.     

Synthesis of tetrasubstituted Zn(II)-phthalocyanines carrying four carboranyl-units as potential BNCT and PDT agents

The synthesis of two tetrasubstituted zinc(II)phthalocyanines carrying four carbon-carbon linked o-carboranyl-units (40 boron atoms, 27.5% boron by weight) is presented. In an in vitro model test the new compounds showed a good photosensitizing efficiency, that encourages further studies for their evaluation as possible BNCT-PDT sensitizers.     

One pot and solvent-free synthesis of 2,9,16,23-tetrachlorometal(II) phthalocyanines

A novel one pot and solvent-free synthesis of 2,9,16,23-tetrachloro metal(II)phthalocyanines in microwave using monosodium salt of 4-chlorophthalate as starting material is described. This method in comparison to conventional route offers high yields (75–92%), eliminates the use of toxic organic solvents, reduces multistep synthesis to one-step, reaction temperature from 190 to 120°C, and reaction time from 5–6 hours to 5 minutes.     

Synthesis and spectral properties of new planar binuclear phthalocyanines sharing the benzene ring

New planar binuclear phthalocyanines sharing the benzene ring were synthesized and their spectral properties were studied. Intense absorption in the near-IR region (∼850 nm) was observed for the first time. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1112–1115, July, 2006.     

Synthesis of tetrathiafulvalene-annulated phthalocyanines

The synthesis of three new TTF-annulated phthalocyanine (Pc) derivatives 5a-c are described. All of them have been characterized by elemental analysis, IR and UV-vis spectroscopy. In all cases, the incorporation of long and flexible aliphatic side-chains into the rigid TTF-annulated Pc core did not promote the formation of a discotic mesophase.     

Synthesis and electronic spectra of dimeric phthalocyanines

Dimeric phthalocyanines of a new type with a bridging 9,9,10,10-tetramethyl-9,10-dihydroanthracene fragment were synthesized. On the basis of X-ray diffraction analysis and molecular modeling of 9,9,10,10-tetramethyl-9,10-dihydroanthracene, a nearly planar structure was assumed for these phthalocyanines. The electronic absorption spectra of the obtained phthalocyanines and their monomeric and conjugated dimeric analogs were compared. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1686–1692, October, 2006.     

Synthesis and properties of new binuclear nickel(ii) phthalocyanines

New binuclear nickel(ii) phthalonitrile complexes, viz., Ni^II 2,2",9(10),9"(10"),17(18),17"(18"),24(25),24"(25")-tetra(phenylene-1,2-dioxy)bisphthalocyanine and Ni^II 2,2",9(10),9"(10"),17(18),17"(18"),24(25),24"(25")-tetra(4-tert-butylphenylene-1,2-dioxy)bisphthalocyanine, were synthesized. The complexes were characterized by electronic spectroscopy and MALDI—TOF mass spectrometry and studied as active components for membranes of ion-selective electrodes in solutions of dicarboxylic acids.     

Studies on tetra-amine phthalocyanines

Metal(II) tetranitro phthalocyanines of cobalt, nickel and copper are synthesized in pure state by a novel modified method. The complexes are characterized using elemental, electronic and IR spectral studies. Pure metal(II) tetra-amino phthalocyanines of cobalt, nickel and copper are synthesized by reducing the nitro groups of the above complexes using sodium sulphide. These complexes are also characterized by elemental, electronic, IR spectral and magnetic susceptibility measurements. The nature of the electrical conductivities of the above three metal(II) tetra-amino phthalocyanine derivatives are studied in the temperature range 303-473 K and the data are presented. Among the effect of various substituent groups on the electrical conducting property of phthalocyanine, amine group substituent on the peripheral benzene ring of the phthalocyanine molecule has been found to increase electrical conductivity to a greatest extent. These complexes showed about 10⁵-10⁶ times higher electrical conductivities compared to their parent phthalocyanine compounds.     

Synthesis and photophysical properties of lead phthalocyanines

This work reports on the synthesis and photophysical parameters of tetra-and octa-substituted new lead phthalocyanines. The complexes synthesized are: 1,4-(tetraphenoxyphthalocyaninato)lead (7a), 1,4-(tetra-tert-butylphenoxyphthalocyaninato)lead (7b), 2,3-(tetraphenoxyphthalocyaninato)lead (8a), 2,3-(tetra-tert-butylphenoxyphthalocyaninato)lead (8b), 2,3-octaphenoxyphthalocyaninatolead (9a) 2,3-[octakis(4-t-butylphenoxyphthalocyaninato)]lead (9b). Photophysical properties were studied for these complexes in a dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.70 to 0.88 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and <10 μs in the rest of the solvents) were observed due to the presence of heavy atom.     

Synthesis and photophysicochemical properties of novel mononuclear rhodium(III) phthalocyanines

Chloro axially-substituted octa(4-isopropylphenoxy)rhodium(III)phthalocyanine, (R)₈PcRhCl (3), was reacted with the nitrogenous bases pyridine (Py) and pyrazine (Pyz) to give the axially-disubstituted octa(4-isopropylphenoxy)rhodium(III)phthalocyanines [(R)₈PcRhCl(L)] (4) and (5), L = (Py) and (Pyz), respectively. In this study, the fluorescence quantum yield (Φ_F), the phosphorescence quantum yield (Φ_phos) and the photodegradation quantum yield (Φ_pd) values for the newly synthesized rhodium phthalocyanine complexes (RhPcs) 4 and 5 are reported. The complexes have also been fully characterized by elemental analysis, FD mass spectrometry, FT-IR and ¹H NMR spectroscopy.     

Convenient and Efficient Method for the Synthesis of Phthalocyanines and Metallophthalocyanines in Task-Specific 2-Hydroxyethyl Ionic Liquids

Tetramerization of substituted phthalonitriles in task-specific 2-hydroxylethyl-based imidazolium and ammonium ionic liquids at 100 °C gave corresponding phthalocyanines in moderate yield. Further the reaction of substituted phthalonitriles in the presence of transition-metal salts in ionic liquids gave the corresponding metallophthalocyanines. The 2-hydroxylethyl ammonium ionic liquids gave better yields of phthalocyanines than 2-hydroxylethyl imidazolium and nonhydroxyl functionalized ionic liquids. The isolation and separations of different phthalocyanines were accomplished by silica-gel column chromatography, and products were characterized by various spectroscopic techniques.     

Synthesis and spectroscopic properties of new water-soluble phthalocyanines containing pyridinium hydrochloride fragments

New 2,9,16,23-tetra[o-(hydroxymethyl)benzyloxy]-substituted phthalocyanines were synthesized. Their reaction with 4-bromopyridine afforded 2,9,16,23-tetra[o-(4-pyridyloxymethyl)benzyloxy]-substituted analogs, treatment of which with HCl led to water-soluble pyridinium salts. Spectroscopic properties of the phthalocyanines obtained were studied and a hypsochromic shift of the Q-band of the hydrochloride as compared with the corresponding pyridinium analogs was observed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2350–2354, December, 2007.     

Synthesis and spectral characteristics of cyclohexylmethoxy-substituted phthalocyanines of rare-earth elements

New symmetrical metal complexes of the rare-earth element phthalocyanines were synthesized by the reaction of 4,5-bis(cyclohexylmethoxy)phthalonitrile, obtained for the first time, with the rare-earth element salts, as well as starting from the corresponding free phthalocyanine. A correlation between method of the synthesis and the reaction product compositions was studied. Structures of the complexes obtained were confirmed by mass spectrometry, X-ray crystallography, and electronic absorption spectroscopy. All the metal complexes are well soluble in organic solvents. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2343–2349, December, 2007.     

Synthesis and photophysical properties of annulated dinuclear and trinuclear phthalocyanines

Metal-free mononuclear, dinuclear and trinuclear phthalocyanines were prepared by a mixed cyclotetramerisation of a 1,2,4,5-tetracyanobenzene derivative and 4,5-bis(2,6-dimethylphenoxy)phthalonitrile. For the first time, a pi-electron-conjugated trinuclear phthalocyanine was synthesised with phthalocyanine units connected by common annulated benzene rings. The Q band of the trinuclear compound in solution occurs at lambda = 944 nm whereas those of the dinuclear and mononuclear compounds are at lambda = 853/830 and 701/664 nm, respectively. Fluorescence quantum yields, fluorescence lifetimes and singlet-oxygen quantum yields of the compounds were determined.     

一种新型含三苯胺的喹啉衍生物及其金属配合物的合成与表征

A new 8-hydroxyquinoline derivative(5)was synthesized and characterized by ESI-MS,~1H NMR spectroscopy,elemental analysis and IR spectroscopy.The photophysical properties of compounds 5,6 and 7 were also deteminedby UV-vis and FL spectroscopy.The vibrational frequency of ligand 5 predicted by using B3LYP method is in goodagreement with experimentally determined values.The compositions of the corresponding copper(Ⅱ)and zinc(Ⅱ)complexes were confirmed to be Cu(C_(29)H_(21)N_2O)_2·H_2O(6)and Zn(C_(29)H_(21)N_2O)_2·H_2O(7)by elementary analysis,thermogravimetry analysis and IR spectroscopy.     

Effect of peripheral substitution on the electronic absorption and fluorescence spectra of metal-free and zinc phthalocyanines

The effect of substituents on the position and intensity of the electronic absorption and fluorescence spectra of phthalocyanines (Pcs) was examined for 35 Pc compounds. When electron-releasing groups are bound to four alpha-benzo positions of the Pc skeleton, the B and Q bands shift to longer wavelength. Relative to this shift, the effect of introducing the same electron-releasing groups at the other four alpha positions amounts to about 1.6-2.0. Although the effect is not always clearly seen, introduction of electron-releasing groups in the beta-benzo positions of the Pc skeleton generally shifts the Q band to shorter wavelength. The effect of electron-withdrawing groups is exactly the opposite with respect to the alpha and beta positions. These effects can be reasonably explained by considering the magnitude of the atomic orbital coefficients of the carbon atoms derived from molecular orbital (MO) calculations. In addition, the following intriguing phenomena were observed in the experiments, although not all were explained theoretically: 1) the splitting of the Q band of metal-free Pcs decreases with increasing wavelength of the Q band, 2) the ring currents of Pcs with Q bands at longer wavelength are generally smaller, and 3) the absorption coefficients of the Q band of Pc compounds with 16-electron-releasing substituents are larger than those of the corresponding tetra- and octasubstituted Pcs by several tens of percent. 4) Our PPP calculations suggested that the absorption coefficient of the Q band of Pcs with more strongly electron releasing substituents is larger. 5) The second HOMO of the Pcs with the Q band at longer wavelength has b(1u) symmetry, as opposed to the a(2u) symmetry of normal Pcs. 6) Pcs showing S1 emission maxima at wavelengths longer than about 740 nm generally have quantum yields of less than 0.1.     

Synthesis and Pd(II) binding studies of octasubstituted alkyl thio derivatised phthalocyanines

Synthesis and characterization of non-peripherally (4,5) and peripherally (6,7) substituted metal free and Pd octapentylthiophthalocyanine and coordination of palladium ions to these Pcs are reported. The unmetalated complexes (4 and 6) show Pd coordination at the central metal and at the ring. The number of Pd ions bound to complex 4 were found to be five and to complex 6 were three. The equilibrium constant for the binding of Pd to complexes 4 was lower (K = 1.2 × 10⁹ dm³ mol⁻¹) than for complex 6 (K = 5.7 × 10¹⁰ dm³ mol⁻¹).     

Synthesis,characterization, and degradation of silicon(IV) phthalocyanines conjugated axially with poly(sebacic anhydride)

A novel silicon(IV) phthalocyanine with two axial poly(sebacic anhydride) chains has been synthesized by melt condensation of silicon phthalocyanine dihydroxide and oligo(sebacic anhydride). The polymer has been spectroscopically characterized and its molecular weights have been determined by gel permeation chromatography (GPC) and ¹H NMR spectroscopy. Nanoparticles with an intensity‐average apparent hydrodynamic radius of 65 ± 1 nm have been prepared from this polymer via a microphase inversion method with sodium dodecyl sulfate as the surfactant. The spherical nanoparticles contain loosely aggregated polymer chains, trapping about 90% of the water. On treatment with NaOH, these nanoparticles undergo degradation that has been monitored by laser light scattering and fluorescence spectroscopy. Because of the axial substitution, the change in the aggregation state of the phthalocyanine core of this polymer during nanoparticle formation and degradation is relatively small compared with that of the zinc(II) phthalocyanine analogue reported earlier, in which poly(sebacic anhydride) chains are linked to the periphery of the phthalocyanine ring. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 837–843, 2005     

4,5-二氮芴-9-酮Cu(II),Zn(II)配合物的合成、晶体结构、热分析及理论计算

合成了 4,5 二氮芴 9 酮 (dafo)的Cu(II) ,Zn(II)配合物 [Cu(dafo) 2 (H2 O) 2 ] (NO3 ) 2 和 [Zn(dafo) 2 (H2 O) 2 ] (NO3 ) 2 ,通过单晶X射线衍射法确定了它们的结构 .晶体结构分析表明 ,配合物分子中Cu(II) ,Zn(II)分别和来自两配体的四个氮原子及两个水分子中的氧原子配位 ,处于六配位的配位环境中 ,两配体基本处于同一平面 ,两水分子垂直于两配体所在平面 ,Cu(II)处于畸变八面体中心 ,Zn(II)处于正常八面体中心 ,对两种配合物进行了元素分析、红外和热分析表征 ,在实验的基础上 ,采用Gaussian 98w中的DFT B3LYP/LANL2DZ对两种配合物进行了全几何优化以及后续计算     

Kinetics and mechanism of the substitution reactions of some monofunctional Pd(II) complexes with different nitrogen-donor heterocycles

Substitution reactions of five monofunctional Pd(II) complexes, [Pd(terpy)Cl]⁺ (terpy = 2,2′;6′,2″-terpyridine), [Pd(bpma)Cl]⁺ (bpma = bis(2-pyridylmethyl)amine), [Pd(dien)Cl]⁺ (dien = diethylenetriamine or 1,5-diamino-3-azapentane), [Pd(Me₄dien)Cl]⁺ (Me₄dien = 1,1,7,7-tetramethyldiethylenetriamine), and [Pd(Et₄dien)Cl]⁺ (Et₄dien = 1,1,7,7-tetraethyldiethylenetriamine), with unsaturated N-heterocycles such as 3-amino-4-iodo-pyrazole (pzI), 5-amino-4-bromo-3-methyl-pyrazole (pzBr), 1,2,4-triazole, pyrazole, pyrazine, and imidazole were investigated in aqueous 0.10 M NaClO₄ in the presence of 10 mM NaCl using variable-temperature stopped-flow spectrophotometry. The second-order rate constants k₂ indicate that the reactivity of the Pd(II) complexes decrease in the order [Pd(terpy)Cl]⁺ > [Pd(bpma)Cl]⁺ > [Pd(dien)Cl]⁺ > [Pd(Me₄dien)Cl]⁺ > [Pd(Et₄dien)Cl]⁺. The most reactive nucleophile of the heterocycles is pyrazine, while the slowest reactivity is with pyrazole. Activation parameters were determined for all reactions and negative entropies of activation, ΔS^≠, supporting an associative mode of substitution. The reactions between [Pd(bpma)Cl]⁺ and 1,2,4-triazole, pzI, and pzBr were also investigated by ¹H NMR to define the manner of coordination. These results could be useful for better explanation of structure-reactivity relationships of Pd(II) complexes as well as for the prediction of potential targets of Pd(II) complexes toward common N-heterocycles, constituents of biomolecules and different N-bonding pharmaceutical agents.