Synthesis of New Metal-Free and Metal-Containing Phthalocyanines with Tertiaryor Quaternary Aminoethyl Substituents

Summary.  A novel phthalodinitrile derivative carrying dimethylaminoethylsulfanyl groups at positions 4 and 5 was synthesized from 2-dimethylaminoethanethiol hydrochloride and 1,2-dichloro-4,5-dicyanobenzene. Its cyclotetramerization in the presence of 2-dimethylamino-ethanol or metal salts (CoCl₂, Zn(OAc)₂) gave metal-free or metal-containing phthalocyanines (M = Co or Zn). These phthalocyanines were converted into water soluble quaternized products by reaction with methyl iodide. The new compounds were characterized by elemental analysis, IR, NMR, and electronic spectra.     

Synthesis and Characterization of New Phthalocyanines Peripherally Fused to Four 13-Membered Tetrathiamacrocycles

The new metal-free phthalocyanine 5 and phthalocyaninatometals 6–8 (M=Co, Ni, or Zn) fused in peripheral positions with four 13-membered tetrathiamacrocycles were prepared by cyclotetramerization of 2, 3, 6, 7, 9, 10-hexahydro-5H-[1, 4, 8, 11]benzotetrathiacyclotridecine-13, 14–dicarbonitrile in the presence of a suitable metal salt or a strong organic base. In contrast to the aza- or oxamacrocycle-fused analogs, the solubility of these phthalocyanines is very low. Complexation of the tetrathiamacrocycles of 7 and 8 with Pd^II or Ag^I to form pentanuclear products was accomplished from their suspensions.     

Synthesis,spectroscopy, electrochemistry and in situ spectroelectrochemistry of partly halogenated coumarin phthalonitrile and corresponding metal-free,cobalt and zinc phthalocyanines

In this study, the preparation of novel 7-hydroxy-3-(2-chloro-4-fluorophenyl)coumarin (1), the ligand, 7-(3,4-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin (2), metal-free phthalocyanine 3 and metallophthalocyanine complexes 4 and 5 (MPcs, M = Co, Zn), β-substituted with 7-oxo-3-(2-chloro-4-fluorophenyl)coumarin functional group was achieved. By the reaction of 7-hydroxy-3-(2-chloro-4-fluorophenyl)coumarin (1) with 1,2-dicyano-4-nitrobenzen in dry DMF as the solvent in the presence of K₂CO₃ as the base, the 7-(3,4-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin (2) was synthesized. Compound 2 reacted with Co(CH₃COO)₂·4H₂O in 2-N,N-dimethylaminoethanol to furnish a novel coumarin containing cobalt(II) phthalocyanine 4. The cyclotetramerization of 2 with Zn(CH₃COO)₂·2H₂O in 2-N,N-dimethylaminoethanol gave the novel coumarin containing Zn(II)phthalocyanine 5; while tetramerization without any metal salts in 2-N,N-dimethylaminoethanol gave the metal-free phthalocyanine 3. The structures of obtained compounds were confirmed by elemental analysis, UV–Vis, IR, MALDI-TOF mass and ¹H NMR spectra. The cyclic and differential pulse voltammetry, and in situ spectroelectrochemistry of 7-oxo-3-(2-chloro-4-fuorophenyl)coumarin substituted phthalocyanines 3, 4 and 5 allowed us to identify metal- and phthalocyanine ring-based redox processes of the complexes.     

Synthesis,electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric characterization of new metal-free and metallophthalocyanines substituted with 4-{2-[2-(1-naphthyloxy)ethoxy]ethoxy} groups

The synthesis of novel metal-free and metallophthalocyanines [Ni(II), Zn(II), Co(II), Cu(II)] were prepared by cyclotetramerization of a novel 4-{2-[2-(1-naphthyloxy)ethoxy]ethoxy}phthalonitrile and the corresponding metal salts (NiCl₂, Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The structures of the target compounds were confirmed using elemental analysis, IR, ¹H NMR, ¹³C NMR, UV–Vis and MS spectral data. Voltammetric and in situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, metal-free, and zinc phthalocyanines show only ring-based reduction and oxidation processes. All complexes decomposed and coated on the electrode as nonconductive film at positive potential window of the electrolyte. An in situ electrocolorimetric method has been applied to investigate color of the electro-generated anionic and cationic forms of the complexes.     

The crystal structure of Mg51Zn20

The crystal structure of Mg₅₁Zn₂₀, a phase designated conventionally as “Mg₇Zn₃,” has been determined by the single-crystal X-ray diffraction method. It was solved by the examination of a Patterson synthesis, and refined by the ordinary Fourier and least-squares method; the R value obtained was 4.8% for 1167 observed reflections. The crystal is orthorhombic, space group Immm, with a = 14.083(3), b = 14.486(3), c = 14.025(3) Å, and Z = 2. There are 18 independent atomic sites, Zn1Zn6, Mg1Mg10, A, and B, and the last two sites are statistically occupied by Zn and Mg atoms with the occupancies; 0.46(2)Zn7 + 0.52(2)Mg11 and 0.24(2)Zn8 + 0.74(2)Mg12, for A and B, respectively. The structure of the crystal is described as an arrangement of icosahedral coordination polyhedra, to which all the atomic sites but Zn3 site belong. In this arrangement the Zn atoms other than the Zn3 and Zn8(B) center the icosahedral coordination polyhedra with coordination number 12. The Zn3, Zn8 atoms, and all the Mg atoms except Mg11(A) are located at the centers of various coordination polyhedra with the coordination numbers from 11 to 15. The distances between neighboring atoms are 2.71–3.07, 2.82–3.65, and 2.60–3.20 Å for ZnZn, MgMg, and ZnMg, respectively.     

Synthesis and characterization of new metal-free and metallophthalocyanines fused α-methylferrocenylmethoxy units

Synthesis of metal-free and metallophthalocyanines bearing α-methylferrocenylmethoxy units was described. Precursor 3 required for the preparation of phthalocyanines 4–9, was synthsized by the nucleophilic aromatic substitution reaction between α-methylferrocenylmethanol and 4-nitrophthalonitrile in dry DMF. The metal-free phthalocyanine 4 was prepared from 4-(α-methylferrocenylmethoxy)phthalonitrile 3 in 1-pentanol with a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Metallophthalocyanines (M = Zn, Cu, Co, Ni and Pb) were prepared by cyclotetramerization reaction of phthalonitrile with appropriate materials. The phthalonitrile, metal-free and metallophthalocyanines were characterized by ¹H and ¹³C NMR, FT-IR UV–Vis and mass spectral data, as well as elemental analyses, which were consistent with the proposed structures.     

Phthalocyanines prepared from 4-chloro-/4-hexylthio-5-(4-phenyloxyacetic acid)phthalonitriles and functionalization of the related phthalocyanines with hydroxymethylferrocene

The phthalonitrile derivative chosen for the synthesis of substituted phthalocyanines [M: 2H, Zn(II), Co(II)] with four chloro and four phenyloxyacetic acid substituents on the periphery is 4-chloro-5-(4-phenyloxyacetic acid)phthalonitrile. The sodium salt of carboxyl substituted zinc phthalocyanine is good soluble in water. Further reactions of zinc and cobalt phthalocyanines bearing phenyloxyacetic acid with thionylchloride gave the corresponding acylchlorides. This functional group reacted with hydroxymethylferrocene in dry DMF to obtain ferrocenyl substituted phthalocyanines. Also chloro substituent in new phthalonitrile was substituted with hexylsulfanyl substituent and its cyclotetramerization in the presence of Zn(AcO)₂·2H₂O and 2-(dimethylamino)ethanol resulted with zinc phthalocyanine. The compounds have been characterized by elemental analysis, MALDI-TOF mass, FT-IR, ¹H NMR, UV-Vis and fluorescence data. Aggregations properties of phthalocyanines were investigated at different concentrations in tetrahydrofuran, dimethylformamide, dimethylsulfoxide, water, and water/ethanol mixture. Also fluorescence spectral properties are reported.     

Synthesis and characterization of novel phthalocyanines bearing quaternizable coumarin

The synthesis of novel metal-free and zinc phthalocyanines with four 3-[(2-diethylamino)ethyl]-7-oxo-4-methylcoumarin dye groups on the periphery were prepared by cyclotetramerization of a novel 3-[(2-diethylamino)ethyl]-7-[(3,4-dicyanophenoxy)]-4-methylcoumarin. The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MALDI-TOF, IR and UV–Vis spectral data. The electronic spectra exhibit bands of coumarin identity along with characteristic Q and B bands of the phthalocyanine (Pc) core. The IR spectra of all the Pcs showed three characteristic intense bands, at 1704 cm⁻¹ for the lactone carbonyl and two bands at 1489–1604 cm⁻¹ for the conjugated olefinic system.     

The synthesis, using microwave irradiation and characterization of novel, metal-free and metallophthalocyanines

The synthesis of novel metal-free (4) and metallophthalocyanines (5, 6, 7 and 8) were prepared by cyclotetramerization of a novel 4-[2-(1-naphthyloxy)ethoxy]phthalonitrile (3). New substitute phthalocyanines showed the enhanced solubility in organic solvents. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis and MS spectral data.     

Chemical behaviour of7Be recoils formed through12C/γ, nα/7Be reaction in several phthalocyanine complexes

The chemical effect of⁷Be recoils formed through a¹²C/, n/⁷Be process from ligand carbon atoms was investigated in a several phthalocyanines. It was found that⁷Be-phthalocyanine was synthesized by⁷Be recoil. Net radiochemical yields of⁷Be-phthalocyanine were estimated to be 10–20% for copper and zinc phthalocyanines, while for metal-free phthalocyanines, yields above 90% were obtained.     

Synthesis,electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric characterization of new phthalocyanines peripherally fused to four flexible crown ether moieties

Novel Ni(II), Zn(II), Co(II) and Cu(II) phthalocyanines with four peripheral 4-[methyleneoxy(18-crown-6)] groups have been synthesized via the cyclic tetramerization of 4-[{(18-crown-6)-yl}methyleneoxy]phthalonitrile and the corresponding metal salts (NiCl₂, Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The thermal stabilities of the metal-free and metallophthalocyanine compounds were determined by thermogravimetric analysis. The structures of the target compounds were confirmed using elemental analysis, IR, ¹H-NMR, ¹³C-NMR, UV–Vis and MS spectral data. Voltammetric and in situ spectroelectrochemical measurements show that while the cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, the metal-free, nickel, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. An in situ electrocolorimetric method has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes.     

Synthesis,characterization and electrochemistry of a new organosoluble metal-free and metallophthalocyanines

4-[2-(Phenylthio)ethoxy]phthalonitrile 3 was synthesized by nucleophilic displacement of nitro group in 4-nitrophthalonitrile with 2-(phenylthio)ethanol 1. The metal-free phthalocyanine 4 was prepared by the reaction of a dinitrile monomer with 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I) phthalocyanines 5, 7, 8 were prepared by reaction of the dinitrile compound with the chlorides of Ni(II), Co(II), Cu(I) in DMAE. Zn(II) phthalocyanine 6, was prepared by reaction of the dinitrile compound with the acetates of Zn(II) in DMAE. Electrochemical behaviours of novel metal-free, Co(II) and Zn(II) phthalocyanines were investigated by cyclic voltammetry, potential differential pulse voltammetry techniques. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis and MS spectral data.     

Synthesis and characterization of novel α- or β-tetra[6,7-dihexyloxy-3-(4-oxyphenyl)coumarin]-substituted metal-free and metallo phthalocyanines

The synthesis of novel phthalonitriles substituted at 3- or 4-position with 6,7-dihexyloxy-3-(4-oxyphenyl)coumarin were performed. The metal-free and metallo phthalocyanines (MPcs) (M = Zn, Co, Cu) were prepared by cyclotetramerization of 6,7-dihexyloxy-3-[p-(2′,3′-dicyanophenoxy)phenyl]coumarin or 6,7-dihexyloxy-3-[p-(3′,4′-dicyanophenoxy)phenyl]coumarin. The newly prepared compounds, phthalonitriles and Pcs, have been characterized by elemental analysis, ¹H NMR, ¹³C NMR, MALDI-TOF, IR, UV–Vis and fluorescence spectral data. The electronic spectra exhibit bands of coumarin identity along with characteristic Q and B bands of the Pc core. The IR-spectra of all Pcs showed three characteristic intense bands at 1709–1700 cm⁻¹ for lactone carbonyl, two bands at 1489–1604 cm⁻¹ for conjugated olefinic system.     

Synthesis of trimethylammoniumphenylthio-substituted phthalocyanines with different pattern of substitution

The base-catalyzed cyclotetramerization of 3-, 4- and 4,5-dimethylaminophenylthio phthalonitriles with zinc(II)acetate afforded 1(4),8(11),15(18),22(25)- and 2(3),9(10),16(17),23(24)-tetrasubstituted and 2,3,9,10,16,17,23,24-octasubstituted Zn(II)phthalocyanines, respectively. The statistical mixed condensation of the same phthalonitriles with 1,2-dicyanobenzene gave the corresponding mono- and disubstituted derivatives. Methylation of such products afforded a series of cationic Zn(II)phthalocyanines with different pattern of substitution, with potential use as photodynamic agents in microbial infections.     

Triphenylphosphinoxid (L) als Solvens und Ligand für Metallphthalocyaninate; Synthese und Struktur von [{Li(L)}2(μ‐pc)], [Li(L)4][Lipc] · Solvat, [Mg(L)pc] · Solvat und [Zn(L)pc] · Solvat

Triphenylphosphine Oxide (L) as Solvent and Ligand for Metallophthalocyaninates; Synthesis and Structure of [{Li(L)}₂(μ‐pc)], [Li(L)₄][Lipc] · Solvate, [Mg(L)pc] · Solvate, and [Zn(L)pc] · Solvate Triphenylphosphine oxide (L) coordinates to metallophthalocyaninates of Li, Mg and Zn at 300 °C. After purification and recrystallization in different solvents the very soluble and stable title compounds have been isolated and structurally characterized. In [{Li(L)}₂(μ‐pc)], the Li atom lies in a distorted tetragonal pyramid of four isoindole N atoms (N_i) at a distance varying between 2.163(5) and 2.301(5) Å, and an O atom at 1.863(5) Å. In [Li(L)₄] · [Lipc] · S, the Li atom of the cation coordinates four O atoms in a distorted tetrahedral arrangement at a distance varying from 1.887(9) to 1.953(9) Å, while the Li atom of the anion is in a quasi quadratic planar geometry of four N_i atoms (1.951(9)–1.977(9) Å) with the Li atom being displaced by 0.15 Å out of the (N_i)₄ plane. The structural data of the distorted tetragonal pyramidale Mg(N_i)₄O moiety in [Mg(L)pc] and the solvates [Mg(L)pc] · S (S = CH₂Cl₂, thf, 2py) generally do not vary significantly: Mg–N_i/2.035(3) –2.061(3) Å, Mg–O/1.955(2)–2.000(3) Å. The Mg atom is displaced by ca. 0.52 Å out of the (N_i)₄ plane towards the O atom and the Mg–O–P moiety is bent (ca. 153°). [Zn(L)pc] · S crystallizes as a mixed crystal of equal parts of the conformer with a bent (155.1(3)°) and that of a quasi linear Zn–O–P moiety (174.2(3)°). Structural data of the Zn(N_i)₄O moiety: (Zn–N_i)_av: 2.024/2.013 Å; Zn–O: 2.050(4)/2.081(4) Å; Zn–(N_i)₄: 0.40/0.33 Å. In the crystal, the Mg and Zn derivates aggregate in double layers forming pairs. The pc ligands in the triclinic complexes with good overlap of the neighbouring pc ligands are in a waving conformation, while those in the monoclinic complexes with weak overlap are in a concave conformation.     

Synthesis and solution properties of new metal-free and metallo-phthalocyanines containing four bis(indol-3-yl)methane groups

Metallo-phthalocyanines bearing four bis(indol-3-yl)methane groups were successfully prepared by reaction of the corresponding phthalonitriles with anhydrous metal salts [Zn(CH₃COO)₂, NiCl₂ and CoCl₂] in the presence of a catalytic amount of DBU in 2-(dimethylamino)ethanol. The metal-free phthalocyanine was obtained by treating a mixture of the phthalonitrile derivative in similar conditions but in the absence of a metal salt. All of these phthalocyanines are soluble in DMSO, DMF, and pyridine. The products were characterized by IR, NMR, and UV-vis spectroscopy, MALDI-TOF-MS, and thermogravimetric analysis. The aggregation properties of the phthalocyanines were investigated at different concentrations in DMSO. All the phthalocyanines showed monomeric behavior in solution.     

Phosphaniminato-Komplexe des Zinks mit Hydrido-, Alkinylo-, Alkenylo- und Amido-Liganden

Phosphoraneiminato Complexes of Zinc with Hydrido, Alkynylo, Alkenylo, and Amido Ligands Synthesis and properties of the phosphoraneiminato complexes [ZnCl(NPMe₃)]₄ ( 1 ), [ZnH(NPMe₃)]₄ ( 2 ) as well as of the alkynylo derivatives [Zn(C≡C–SiMe₃)(NPMe₃)]₄ ( 3 ), [Zn(C≡C–C≡C–SiMe₃)(NPR₃)]₄ [R = Me ( 4 a ), R = Et ( 4 b )], [Zn(C≡C–Ph)(NPMe₃)]₄ ( 5 ) and of the alkenylozinc complexes [Zn(CH=CHMe)(NPR₃)]₄ [R = Me ( 6 a ), R = Et ( 6 b )] are described. According to crystal structure analyses of 1 , 3 , and 4 b these complexes possess heterocubane structures with only slightly distorted Zn₄N₄ cubic skeletons. Experiments to substitute the terminal ligands at the zinc atoms by bis(trimethylsilyl)amido groups lead to disintegration of the heterocubanes and formation of the dimeric complex [Zn(μ₂-NPEt₃){N(SiMe₃)₂}]₂ ( 7 ) and of the trinuclear derivative [Zn₃(μ₂-NPMe₃)₄{N(SiMe₃)₂}₂] ( 8 ), in which the central zinc atom is surrounded by the four N atoms of the NPEt₃^– groups in a spiro-cyclic fashion. 7 and 8 are also characterized by crystal structure analyses.     

The synthesis and characterization of new metal-free and metallo phthalocyanines substituted with four dithiatetraoxa macrocyclic moieties

New metal-free phthalocyanine (7) fused symmetrically in peripheral positions with four dithiatetraoxa macrocycles, has been synthesized by cyclotetramerization of the isoindolinediimine derivative of macrocyclic 6. Metallophthalocyanine (8) was synthesized by reaction of phthalonitrile derivative (5) with anhydrous nickel(II) chloride. The new compounds were characterized by elemental analysis, ¹H and ¹³C-NMR, IR UV–Vis and mass spectroscopies.     

Effects of coumarin substituents on the photophysical properties of newly synthesised phthalocyanine derivatives

In this study, synthesis of new ligands, 8-hydroxy-3-[p-(3′,4′-dicyanophenoxy)-phenyl]coumarin and 8-hexyloxy-3-[p-(3′,4′-dicyanophenoxy)-phenyl]coumarin, and their phthalocyanines, 2,9,16,23-tetrakis[8-hexyloxy-3-(4-oxyphenyl)coumarin]-metal-free and metallophthalocyanines {M[Pc(OBzCou)₄] (M = 2H, Zn(II), Co(II); Bz: benzene; Cou: coumarin)} were synthesised. The novel chromogenic compounds were characterised by elemental analysis: ¹H NMR, ¹³C NMR, MALDI-TOF, IR and UV–vis spectral data. The effect of coumarin substituents on the photophysical properties of metal-free (H₂Pc) and zinc phthalocyanines (ZnPc) derivatives has been examined. Spectrophotometric measurements revealed that coumarin-substituted ZnPc derivatives were in the unaggregated form, whereas those of H₂Pc species were in aggregated form. It means that substitution of coumarin derivative prevents the cluster formation in the presence of zinc ion in the centre of Pc.     

Synthesis and electrochemistry of new octa-substituted metal-free and metallophthalocyanines

The synthesis and characterization of metal-free (H₂-Pc) and metal-containing (Zn, Co, and Cu) derivatives of a symmetrically octa-substituted phthalocyanine derived from 4,5-bis[2-(phenylthio)ethoxy]phthalonitrile were carried out by microwave irradiation. The electrochemical properties of the metal-free phthalocyanine 4 and metallophthalocyanine complexes 5 and 6 were investigated by cyclic voltammetry and differential pulse voltammetry. We have previously investigated the electrochemical properties of the tetra substituted 2-(phenylthio)ethoxy phthalocyanines. The reduction potential of the octa-substituted metal-free phthalocyanine shifted to more negative potential as a result of the electron donating of the 2-(phenylthio)ethoxy groups on the periphery compared to those of tetra substituted. The H₂Pc and ZnPc demonstrated ligand-based electron transfer processes, while CoPc complex has a metal-based reduction process. Similar aggregation behavior was observed for octa-substituted phthalocyanines. The compounds were characterized using IR, ¹H NMR, ¹³C NMR, elemental analysis, and MS spectral data.