Selective synthesis of clamshell-type bis-phthalocyanine bearing tetrachlorocyclotriphosphazene intramolecular bridge

The selective synthesis of clamshell-type bis-phthalocyanine was performed using cyclotriphosphazene as a peripheral spacer. The spectral characteristics of the target dye are similar to those of most H-dimers, and the reaction can be considered conditionally selective with respect to the cis-isomer     

Selective synthesis of binuclear N-substituted tetrazoles and tetrazolium salts

The selective alkylation of mononuclear tetrazoles by 2,5-dimethyl-2,5-hexanediol and of N-unsubstituted binuclear tetrazoles by tert-butyl alcohol was realized in perchloric and sulfuric acids. A series of previously unknown N-substituted binuclear tetrazoles and tetrazolium salts were synthesized. Data from X-ray crystallographic analysis of 2,5-dimethyl-2,5-di(5-phenyl-2-tetrazolyl)hexane are presented.Scientific-Research Institute of Physicochemical Problems, Belorus State University, Minsk; e-mail: fhp@fhp.bsu.unibel.by. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 387–395, March, 2000.     

Heteroligand and heteronuclear clamshell-type phthalocyanines: selective preparation, spectral properties, and synthetic application

A direct synthetic method to produce heteronuclear and heteroligand clamshell-type binuclear phthalocyanines via a nucleophilic coupling reaction between A₃B-type monophthalocyanines is developed with the target compounds demonstrating the possibility to form sandwich-type heterocomplexes for the first time.     

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.     

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.     

The synthesis and electrochemical behaviour of carbazole-substituted phthalocyanines

The syntheses of new cobalt and zinc phthalocyanine complexes containing carbazole (Cz) substituents at the peripheral positions are reported (CzCoPc and CzZnPc). The reaction of Cz with 4-iodophthalonitrile in the presence of a catalytic amount of copper(I) oxide and potassium carbonate led to the formation of 4-(9H-carbazol-9-yl) phthalonitrile. Furthermore, by heating the dinitrile and anhydrous metal salts (CoCl₂, Zn(CH₃COO)₂) at 160 °C in n-hexanol in the presence of DBU, the phthalocyanines were obtained. They were characterised by ¹H NMR, FT-IR, UV-Vis and MS spectroscopic data. Aggregation behaviours of Pcs were investigated in THF. Electrochemical redox behaviour of CzCoPc was investigated by cyclic voltammetry depending on the potential range, and the oxidation and reduction products were followed by UV-Visible absorption measurements. Polymerisation of CzCoPc was carried out by potentiodynamic methods on glassy carbon electrode, and the catalytic activity of resulting polymer (P[CzCoPc]) was tested comparatively with polycarbazole (PCz)-coated electrode for dopamine and better response was obtained for P[CzCoPc] modified electrode.     

A comparative DFT study of oxygen reduction reaction on mononuclear and binuclear cobalt and iron phthalocyanines

The oxygen reduction reaction (ORR) catalyzed by mononuclear and planar binuclear cobalt (CoPc) and iron phthalocyanine (FePc) catalysts is investigated in detail by density functional theory (DFT) methods. The calculation results indicate that the ORR activity of Fe-based Pcs is much higher than that of Co-based Pcs, which is due to the fact that the former could catalyze 4e^- ORRs, while the latter could catalyze only 2e^- ORRs from O₂ to H₂O₂. The original high activities of Fe-based Pcs could be attributed to their high energy level of the highest occupied molecular orbital (HOMO), which could lead to the stronger adsorption energy between catalysts and ORR species. Nevertheless, the HOMO of Co-based Pcs is the ring orbital, not the 3d Co orbital, thereby inhibiting the electron transfer from metal to adsorbates. Furthermore, compared with mononuclear FePc, the planar binuclear FePc has more stable structure in acidic medium and more suitable adsorption energy of ORR species, making it a promising non-precious electrocatalyst for ORR.     

Microwave-assisted synthesis and reverse saturable absorption of phthalocyanines and porphyrins

Soluble phthalocyanines, including tetrakis(2,9,16,23-cumylphenoxy) copper phthalocyanines (CuPc(β-CP)₄), tetrakis(1,8,15,22-cumylphenoxy) copper phthalocyanines (CuPc(α-CP)₄) as well as tetrakis(2,9,16,23-tert-butyl) copper phthalocyanines (CuPc(β-t-butyl)₄), and porphyrins (5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrins; M(TBP), M=H₂, Zn, Cu, Mg, InCl, AlCl) have been quickly synthesized by microwave irradiation. Furthermore, their reverse saturable absorption have also been investigated by dissolving them in solvent or incorporating them in polymer-silica hybrid material with a sol-gel process with polyvinyl butyral and tetraethyl orthosilicate as precursors. A new method for the preparation process of phthalocyanines and porphyrins in the solids has been successfully used.     

Selective synthesis of meso-naphthylporphyrins

A series of novel meso-(8-substituted naphth-1-yl)porphyrins has been synthesized creating derivatives with a tight recognition environment above the porphyrin plane. The selective synthesis of single atropisomers is discussed. Condensation of bisnaphthaldehyde 12 with phenyldipyrromethane unexpectedly led to selective synthesis of the alpha,alpha-5,10-bridged isomer 14. A mechanism is proposed for this unusual scrambling, and alternative syntheses of alpha,alpha-5,15-bisnaphthylporphyrins are described. Synthesis of 5,15-analogues can be achieved by employing (pentafluorophenyl)dipyrromethane or via presynthesis of a bis(dipyrromethane) derivative 22 (from bisnaphthaldehyde 12) and subsequent condensation with benzaldehyde.     

Solid-phase synthesis of asymmetrically substituted "AB3-type" phthalocyanines

Synthesis of phthalocyanines with asymmetrical substitution on the periphery is often difficult due the problems in purification of the phthalocyanine mixtures obtained. Using a poly(ethylene glycol) (PEG)-based support with a Wang-type linker, we have developed the synthesis of monohydroxylated, oligoethylene glycol substituted phthalocyanines utilizing an amidine-base-promoted phthalonitrile tetramerization reaction. The use of a hydrophilic support allows symmetrical phthalocyanine product formed in solution to be readily and completely removed by washing while leaving the "AB3" product on the support. Acid cleavage with 10% trifluoroacetic acid provides the pure unsymmetrically substituted Pc. This method was applied to several metallo Pcs. Additionally, methods to avoid premature reactions on-resin that give A2B2 products are provided.     

The synthesis and characterization of new phthalocyanines containing hexaazadithia macrobicyclic moieties

The new metal-free and metallo phthalocyanines (4) and (5) bearing four tetrasubstituted hexaazadithia macrobicycles on peripheral positions, have been synthesized. Phthalonitrile (3) has been synthesized from the reaction of (1,3,6,9,11,14 hexaazatricyclo [12.2.1.1^6,9]) (1) and 1,2-bis(2-iodomercaptoethyl)-4,5-dicyanobenzene (2). The new compounds were characterized by elemental analysis, and IR, ¹H, ¹³C-NMR, UV-Visible and mass spectral data.     

Site-specific synthesis of oxo-bridged mixed-valence binuclear complexes on mesoporous silica

We report the site-specific synthesis of mixed valence TiIV-O-FeII complexes within the pores of ordered mesoporous silica (SBA-15). By using 6-di- tert-butylpyridine as the selective activator of tripodally linked TiIV-OH groups of Ti-grafted SBA-15, the FeCl2.4H2O complexes reacted selectively with the nucleophilic TiIV-O(-) groups. The formation of Si-O-FeII byproducts, due to the reaction with the abundant Si-OH groups, was successfully restricted and the selectivity for forming the TiIV-O-FeII complexes exceeded 80%. The metal-metal interaction of TiIV-O-FeII complexes was confirmed by the appearance of TiIV/FeII --> TiIII/Fe III metal-to-metal charge transfer band, and their coordination, valency, and spin state were characterized by diffuse transmission UV-vis, Fourier transform IR, and Fe K-edge X-ray absorption fine structure measurements. It was also confirmed that the present methods can be extended to other metal combinations of TiIV-O-NiII and TiIV-O-MnII. The electron transfer processes occurring under photoinduced metal-to-metal charge transfer of oxo-bridged mixed valence complexes on silica supports have recently been proven as a new class of visible-light-sensitive redox centers. Thus, the present synthetic procedure allows the fabrication of a variety of photochemical reaction centers according to the molecular-level design.     

Investigation of binuclear metal phthalocyanines as electrocatalysts for Li/SOCl<Subscript>2</Subscript> battery

Three novel series of the binuclear metal phthalocyanines M₂Pc₂, M₂Pc₂Hc, and M₂Nc₂ (M?=?Mn(II), Fe(II), Co(II), Ni(II), and Cu(II)) were synthesized and characterized. The electrocatalytic performance of the binuclear compounds to lithium–thionyl chloride battery was evaluated by operating these compounds in the electrolyte of the battery. The results indicated that the binuclear metal phthalocyanines improved the capacity of the battery by an increase of approximately 30–58 %. Of all, Cu₂Pc₂Hc and Fe₂Nc₂ displayed the highest increments of 56 and 57 %, respectively.     

Effect of metal phthalocyanines on the synthesis and physicochemical properties of polyaniline

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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.     

Dendritic phthalocyanines: synthesis,photophysical properties,and aggregation behavior

This mini-account describes our recent effort to exploit dendritic phthalocyanines, focusing on their photophysical properties and aggregation behavior in water and in microheterogeneous media. Two series of dendritic phthalocyanines have been prepared. The ones with terminal ester functionalities are non-aggregated in common organic solvents, exhibiting an intramolecular singlet-singlet energy transfer from the excited aryl-containing dendrons to the phthalocyanine core. The other series contain terminal carboxylate groups of which the aggregation tendency in water decreases as the size of the dendron increases. The lower-generation analogues are susceptible to surfactants, in particular the cationic n-hexadecyltrimethylammonium bromide (CTAB), and poly(ethylene oxide) (PEO), which are very effective to disrupt the molecular aggregation of phthalocyanines. The interactions have been monitored by absorption and fluorescence spectroscopy together with laser light scattering. The photophysical properties of the dendrimer/PEO complexes have also been studied by transient spectroscopy. To cite this article: D.K.P. Ng, C. R. Chimie 6 (2003).