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 of unsymmetrically substituted dodecakis(trifluoroethoxy)-phthalocyaninato vanadyl complexes

Three novel unsymmetrical vanadyl dodecakis(2,2,2-trifluoroethoxy)phthalocyaninates with nitro, amino or with no substitution were synthesized by a statistical condensation of 3,4,5,6-tetrakis(2,2,2-trifluoroethoxy)phthalonitrile with 4-nitro, 4-amino or 4-unsubstituted phthalonitrile, and separated by common column chromatography. These highly soluble phthalocyanines were characterized by elemental analysis, ir and ¹H-nmr, uv-visible and fast-atom-bombardment mass spectroscopy. Their uv-visible absorption spectra in solution and in doped poly(methyl methacrylate) films showed that they were less aggregated unsymmetrical phthalocyanines.     

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.     

Synthesis of novel unsymmetrical phthalocyanines substituted with crown ether and nitro groups

This work reports on the synthesis of new unsymmetrically substituted phthalocyanines (M = Zn, Cu, Co, Ni) bearing three benzo-15-crown-5 units through oxy bridges and a nitro group. Phthalocyanines were prepared by a statistical condensation of 4-nitro phthalonitrile and 1-{[(benzo-15-crown-5)-4′-yl]oxy}phthalonitrile in the presence of anhydrous metal salts. All the target unsymmetrical phthalocyanines were separated by column chromatography and characterized elemental analyses, ¹H NMR, IR, mass and UV–Vis spectral data. Electrochemical behaviors of Cu (II) phthalocyanine by cyclic voltammetry and differential pulse voltammetry techniques gave two common phthalocyanine ring reductions and one ring oxidation processes. Peak-to-peak separation of the processes II and III (388 mV) and the measure of gap (1.672 V) between the HOMO and LUMO for the complex, fits a phthalocyanine with electrochemically inactive metal center.     

Oxidation of benzyl alcohol by novel peripherally and non-peripherally modular C2-symmetric diol substituted cobalt (II) phthalocyanines

In this study, a modular ligand structure was designed by altering the binding position of the phenyl group at backbone of hydrobenzoin. A series of regio isomeric substituted phthalonitriles derived from this modular C₂-symmetric ligand was synthesized and characterized. Then, eight cobalt (II) phthalocyanines (CoPc) were obtained from the reaction of phthalonitrile derivatives with cobalt (II) chloride. The catalytic activities of synthesized cobalt (II) phthalocyanines were tested for benzyl alcohol oxidation in acetonitrile using tert-butylhydroperoxide as the oxygen source and in the presence of N-bromosuccinimide as an additive at 80 °C for 5 hr of the reaction. In this sense, the effect of substrate to catalyst ratio and oxidant to catalyst ratio have been studied in detail for getting the highest benzaldehyde selectivity (up to 83%). The effect of structural design of substituents at peripheral or non-peripheral positions of phthalocyanine skeleton on the catalytic activity performance of cobalt (II) phthalocyanines in benzyl alcohol oxidation was also clarified. All newly synthesized compounds are characterized by FT-IR, ¹H NMR, IR, UV–Vis and MALDI-TOF MS spectral data.     

Metallophthalocyanines with rod-shaped substituents

4-(4′-Dioctylaminocarbonylbiphenyloxy) phthalonitrile was synthesized from 4-(4′-carboxybiphenyloxy)phthalonitrile and dioctylamine in the presence of Et₃N. Metallophthalocyanines (Zn, Co and Cu) substituted with four dioctylaminocarbonyl biphenyloxy groups on the peripheral positions were prepared from 4-(4′-dioctylaminocarbonylbiphenyloxy)phthalonitrile and the corresponding divalent metal salts (Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The new phthalocyanines are soluble in common organic solvents. These compounds were characterised by ¹H-NMR, ¹³C-NMR, FT-IR, UV-Vis and mass spectroscopies.     

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.     

Synthesis and characterization of a new organo-soluble metal-free and metallophthalocyanines bearing flexible moieties

This paper describes a new symmetric metal-free phthalocyanine and its transition metal complexes which were prepared by a condensation of 1,2-dihydroacenaphthylen-1-ol 1 and 4-nitro phthalonitrile 2 with Co(II), Ni(II), Cu(II), and Zn(II) salts in 2-(dimethylamino)ethanol, respectively. The novel phthalocyanines bearing oxygen donor atoms on peripheral position have been characterized by IR, UV-Vis, ¹H NMR, ¹³C NMR, Mass spectra and elemental analysis. The thermal behaviours of 4-8 were investigated by TG/DTA.     

Synthesis of new highly organosoluble metallophthalocyanines with 1,8-dioxo-octahydroxanthene substituents

New highly organosoluble metallophthalocyanines (M = Zn, Co, Ni and Cu) bearing four [4-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenoxy] substituents at peripheral positions have been prepared by tetramerization of 4-[4-(3,3,6,6-tetramethyl-1,8-dioxo-dodecahydro-1H-xanthen-9-yl)phenoxy]phthalonitrile in 2-(dimethylamino)ethanol using microwave irradiation or conventional heating. Ni(II), Co(II), and Cu(I) chloride were employed in order to synthesize the corresponding metal phthalocyanines and Zn(OAc)₂ was used for the preparation of the zinc phthalocyanines. 4-[4-(3,3,6,6-Tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenoxy]phthalonitrile was obtained by nucleophilic displacement of the nitro group in 4-nitrophthalonitrile with 9-(4-hydroxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7-tetrahydro-2H-xanthene-1,8(5H,9H)-dione. 9-(4-Hydroxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7-tetrahydro-2H-xanthene-1,8(5H,9H)-dione was synthesized efficiently from dimedone and 4-hydroxybenzaldehyde. All the phthalocyanines are soluble in DMSO, DMF, CHCl₃, THF, CH₂Cl₂, and CH₃CN. The new compounds were characterized by IR, NMR, and UV–vis spectroscopy, elemental analysis, and thermogravimetric analysis.     

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.     

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.     

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.     

Synthesis,characterization, and determination of photophysicochemical properties of peripheral and nonperipheral tetra‐7‐oxy‐3,4‐dimethylcoumarin substituted zinc,indium phthalocyanines

The photochemical and photophysical properties of peripheral and nonperipheral zinc and indium phthalocyanines containing 7‐oxy‐3,4‐dimethylcoumarin synthesized were investigated in this study. 7‐Hydroxy‐3,4‐dimethylcoumarin ( 1 ) was synthesized via Pechmann condensation reaction and then the phthalonitrile derivatives [4‐(7‐oxy‐3,4‐dimethylcoumarino)phthalonitrile ( 2 ) and 3‐(7‐oxy‐3,4‐dimethylcoumarino)phthalonitrile ( 3 )] were synthesized by nucleophilic aromatic substitution. Phthalocyanine compounds containing coumarin units on peripheral ( 4 and 5 ) and nonperipheral ( 6 and 7 ) positions were prepared via cyclotetramerization of phthalonitrile compounds. All compounds' characterizations were performed by spectroscopic methods and elemental analysis. The phthalocyanine derivatives' ( 4–7 ) photochemical and photophysical properties were studied in DMF. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines ( 4 – 7 ) were studied in DMF. They produced good singlet oxygen (e.g., Φ_Δ = 0.93 for 7 ) and showed appropriate photodegradation (in the order of 10^?5), which is very important for photodynamic therapy applications.     

Synthesis,Characterization, and Investigation of Cholinesterase Inhibitory Properties of Novel Phthalocyanines

In this study, 4‐{2‐(2‐thienyl)ethoxy}phthalonitrile ( 3 ) and its tetra substituted peripherally metal‐free ( 4 ), lead (II) ( 5 ), magnesium (II) ( 6 ), and cobalt (II) ( 7 ) phthalocyanines were synthesized. The structural characterization of the obtained compounds was performed by a combination of FTIR, ¹H‐NMR, UV–vis, and MALDI‐TOF techniques. The inhibitory properties of these compounds were determined using Ingkaninan's methods against cholinesterase enzymes. Compound ( 7 ) had the highest enzyme inhibitory effect toward AChE and BuChE enzymes with IC₅₀ values of 23.71 ± 0.39 and 27.29 ± 0.22 μM, respectively. The enzyme kinetic study of compound ( 7 ) demonstrated noncompetitive AChE inhibition and uncompetitive BuChE inhibition. The K_i values of compound ( 7 ) against AChE and BuChE were found to 39.15 and 7.25 μM, respectively. In the tested compounds, ( 7 ) deserves further investigation for potential therapeutic candidates of Alzheimer's disease.     

Octakis(dodecyl)phthalocyanines: Influence of Peripheral versus Non-Peripheral Substitution on Synthetic Routes,Spectroscopy and Electrochemical Behaviour

Non-peripherally octakis-substituted phthalocyanines (npPc’s), MPc(C₁₂H₂₅)₈ with M = 2H (3) or Zn (4), as well as peripherally octakis-substituted phthalocyanines (pPc’s) with M = Zn (6), Mg (7) and 2H (8), were synthesized by cyclotetramerization of 3,6- (2) or 4,5-bis(dodecyl)phthalonitrile (5), template cyclotetramerization of precursor phthalonitriles in the presence of Zn or Mg, metal insertion into metal-free phthalocyanines, and removal of Mg or Zn from the phthalocyaninato coordination cavity. The more effective synthetic route towards pPc 8 was demetalation of 7. npPc’s were more soluble than pPc’s. The Q-band λ_max of npPc’s was red-shifted with ca. 18 nm, compared to that of pPc’s. X-ray photoelectron spectroscopy (XPS) differentiated between N–H, N_meso and N_core nitrogen atoms for metal-free phthalocyanines. Binding energies were ca. 399.6, 398.2 and 397.7 eV respectively. X-ray photoelectron spectroscopy (XPS) also showed zinc phthalocyanines 4 and 6 have four equivalent N_meso and four equivalent N–Zn core nitrogens. In contrast, the Mg phthalocyanine 7 has two sets of core N atoms. One set involves two N_core atoms strongly coordinated to Mg, while the other encompasses the two remaining N_core atoms that are weakly associated with Mg. pPc’s 6, 7, and 8 have cyclic voltammetry features consistent with dimerization to form [Pc][Pc⁺] intermediates upon oxidation but npPc’s 3 and 4 do not. Metalation of metal-free pPc’s and npPc’s shifted all redox potentials to lower values.     

13C NMR spectra of bicyclo[3.3.1]nonanones and their derivatives

Conclusions An assignment was made of the lines in the¹³C NMR spectra of the mono- and diketones of the bicyclo[3.3.1]nonane series, and of the hydrolysis products of bicyclo[3.3.1]nonane-2,9-dione and its 7-benzoyloxy derivative.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2386–2389, October, 1979.     

Fourier transform NMR investigations of 13C labeled silyl and stannyl acetylenes

The ¹³C NMR spectra of ¹³C labeled mono- and di-substituted silyl- and stannyl-acetylenes have been studied. It was found that the values of ¹J(CC) coupling constants between acetylenic carbons decrease very sharply in the series Alk₃SiCCH, Alk₃SnCCH, Alk₃SiCCSiAlk₃ and Alk₃SnCCSnAlk₃. These results and the observed changes in the geminal hetero-atom β-acetylenic carbon couplings suggest a very strong p_πd_π interaction between the π-electrons of the triple bond and the vacant d orbitals of silicon and tin.     

Synthesis and photophysical properties of metal free, titanium, magnesium and zinc phthalocyanines substituted with a single carboxyl and hexylthio groups

2,3,9,10,16,17,23,24-Octakis(hexylthio)phthalocyanines (4a-6a) and 2-carboxy-9,10,16,17,23,24-hexakis(hexylthio)phthalocyanines (4b-6b) were synthesized using a one-pot method by cyclotetramerization of the phthalonitriles: 4,5-bis(hexylthio)phthalonitrile and carboxylic acid phthalonitrile. 2-Carboxycatecholato-2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyaninatotitanium(IV) (8) was prepared from 2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyaninatooxotitanium(IV) (7). The structures of these compounds were characterized by using elemental analyses, UV-Vis, FT-IR, ¹H NMR and mass spectroscopies. Their photophysical properties were also studied. The Φ_F values are 0.12, 0.02, 0.10, 0.06, 0.10, 0.06, 0.65, 0.80 and the Φ_T values are 0.58, 0.56, 0.57, 0.64, 0.22, 0.48, 0.17, 0.12 for 4-8, respectively. The Φ_F value for complex 8 is higher than ever reported for phthalocyanine complexes. The triplet lifetimes (τ_T) values for all the complexes were generally good, ranging from 50 to 310 μs, and generally increased in the presence of the single carboxyl group. These complexes showed reasonable triplet quantum yields and lifetimes, and hence have potential for use as photosensitizers in photodynamic therapy (PDT) of cancer.     

Multinuclear NMR studies on substituted derivatives of Rh6(CO)16 in solution

Multinuclear NMR data (¹³C, ³¹P, ¹³C–{³¹P}, ¹³C–{¹⁰³Rh} and ³¹P–{¹⁰³Rh}) for a series of mono- and di-substituted derivatives of Rh₆(CO)₁₆ containing neutral two electron donor ligands [Rh₆(CO)₁₅L, (L=NCMe, py, cyclooctene, PPh₃, P(OPh)₃,1/2(μ₂,η¹:η¹-dppe)); Rh₆(CO)₁₄(LL), (LL=cis-CH₂=CMe-CMe=CH₂, dppm, dppe, (P(OPh)₃)₂)] are reported; these data show that the solid state structure is maintained in solution. Detailed assignments of the ¹³CO NMR spectra of Rh₆(CO)₁₅(PPh₃) and Rh₆(CO)₁₄(dppm) clusters have been made on the basis ¹³C–{¹⁰³Rh} double resonance measurements and the specific stereochemical features of the observed long range couplings in these clusters have been studied. The stereochemical dependence of ³J(P–C) for terminal carbonyl ligands is discussed and the values of ³J(P–C) are found to be mainly dependent on the bond angles in the P–Rh–Rh–C fragment; these data enable the fine structure of the complex multiplets in the ¹³C–{¹H} and ³¹P–{¹H} NMR spectra of Rh₆(CO)₁₄ (dppm) to be simulated. Variable temperature ¹³C–{¹H} NMR measurements on Rh₆(CO)₁₅(PPh₃) reveal the carbonyl ligands in this complex to be fluxional. The fluxional process involves exchange of all the CO ligands except the two terminal CO's associated with the rhodium trans to the substituted rhodium and can be explained by a simple oscillation of the PPh₃ on the substituted rhodium atom aided by concomitant exchange of the unique terminal CO on this rhodium with adjacent μ₃-CO's.     

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.