Ali Erdoğmuş

Photophysical and photochemical properties of novel phthalocyanines bearing non-peripherally substituted mercaptoquinoline moiety

The synthesis, photophysical and photochemical properties of nonperipherally (α) mercaptoquinoline substituted Zn(II), TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.

Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties

The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, (1)H and (11)B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ=0.41, 0.39).

Highly soluble 3,4-(dimethoxyphenylthio) substituted phthalocyanines: Synthesis, photophysical and photochemical studies

The synthesis of a new 3,4-(dimethoxyphenylthio) substituted phthalonitrile (1) and its soluble metal free (2), zinc (II) (3), oxo-titanium (IV) (4) and nickel (II) (5) phthalocyanine derivatives are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, (1)H NMR, UV-Vis, fluorescence spectroscopies and mass spectra. General trends are described for fluorescence, photodegradation and singlet oxygen quantum yields and fluorescence lifetimes of oxo-titanium (IV) and zinc (II) phthalocyanine compounds in dimethylsulfoxide (DMSO). The effects of the metal ion on the photophysical and photochemical parameters for these phthalocyanines (3 and 4) are also reported.

The Synthesis, Characterization, Crystal Structure and Photophysical Properties of a New Meso-BODIPY Substituted Phthalonitrile.

A new highly fluorescent difluoroboradipyrromethene (BODIPY) dye (4) bearing an phthalonitrile group at meso-position of the chromophoric core has been synthesized starting from 4-(4-meso-dipyrromethene-phenoxy)phthalonitrile (3) which was prepared by the oxidation of 4-(2-meso-dipyrromethane-phenoxy)phthalonitrile (2). The structural, electronic and photophysical properties of the prepared dye molecule were investigated. The final product exhibit noticeable spectroscopic properties which were examined by its absorption and fluorescence spectra. The original compounds prepared in the reaction pathway were characterized by the combination of FT-IR, 1H and 13C NMR, UV–vis and MS spectral data. It has been calculated; molecular structure, vibrational frequencies, 1H and 13C NMR chemical shifts and HOMO and LUMO energies of the title compound by using B3LYP method with 6-311++G(dp) basis set, as well. The final product (4) was obtained as single crystal which crystallized in the triclinic space group P-1 with a = 9.0490 (8) Å, b = 10.5555 (9) Å, c = 11.7650 (9) Å, α = 77.024 (6)°, β = 74.437 (6)°, γ = 65.211 (6)° and Z = 2. The crystal structure has intermolecular C—H···F weak hydrogen bonds. The singlet oxygen generation ability of the dye (4) was also investigated in different solvents to determine of using in photodynamic therapy (PDT).

Novel sulfonated hydrophilic indium(III) and gallium(III) phthalocyanine photosensitizers: preparation and investigation of photophysicochemical properties

Abstract The new tetra-non-peripherally benzenesulfonic acid-substituted hydrophilic gallium chloride and indium chloride phthalocyanine complexes have been synthesized by cyclotetramerization of 4-(2,3-dicyanophenyl)benzenesulfonic acid (1). The newly synthesized phthalocyanines have been characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, mass and UV–vis spectroscopy techniques. The water-soluble gallium(III) phthalocyanine derivative (2) was aggregated in aqueous media but was fully disaggregated in the presence of a surfactant Triton X-100. The incorporation of sulfonate moieties of the phthalocyanine macrocycle provides hydrophilic character to the new compounds, which is useful for drug administration and serves as crucial in PDT application. So, the photochemical properties (singlet oxygen quantum yields and photodegradation quantum yields) and photophysical properties (fluorescence behavior) of the complexes were reported in different solutions (DMSO and water). The results of spectral measurements showed that both np-GaPc (2) and np-InPc (3) can be used as sensitizers in PDT because of their singlet oxygen efficiencies.

Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II) phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO), dimethylformamide (DMF), and tetrahydrofurane (THF). Among the different substituents, phthalocyanines with cinnamaldimine moieties (1c and 2c) have the highest singlet oxygen quantum yields () and those with nitro groups (1a and 2a) have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II) phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ) in these solvents.

Novel peripherally substituted zinc phthalocyanine: synthesis, characterization, investigation of photophysicochemical properties and theoretical study

Abstract The new thiohexanoic acid substituted zinc phthalocyanine was synthesized and characterized by FT-IR, 1H–NMR, electronic spectroscopy, and mass spectrometry as well as DFT calculation studies. The photochemical properties (singlet-oxygen quantum yields and photodegradation quantum yields) and photophysical properties (fluorescence quantum yields and fluorescence behavior) of the compound were studied in dimethylsulfoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF). Singlet-oxygen quantum yields ranged from 0.29 to 0.43. However, energy-minimized structure, vibrational frequency, electronic distribution and molecular orbitals were obtained by DFT calculations which were supported by experimental results.

Novel indium(III) phthalocyanines; synthesis, photophysical and humidity sensing properties

Three new 3,4-(dimethoxyphenylthio) (4), 4-(thiophen-3yl)phenoxy (5), 3,4-(methylendioxy)phenoxy (6) substituted chloroindium(III) phthalocyanines were synthesized and characterized. The indium(III) phthalocyanine derivatives were characterized by using spectroscopy methods, FT-IR, 1H-NMR spectroscopy, electronic spectroscopy and mass spectra as well as elemental analysis. The photophysical properties (fluorescence quantum yields and fluorescence behavior) of their peripherally tetra-substituted new complexes (4 to 6) have been examined. General trends focus on fluorescence behavior, photophysical and electronic properties as well as the humidity sensing ability of these compounds in dimethylsulfoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF). Complexes (4 to 6) showed reasonably higher fluorescence quantum yields ranging from 0.050 to 0.092 in DMF, 0.029 to 0.084 in DMSO and 0.023 to 0.060 in THF compared to other indium derivatives in the literature. The nature of the substituent and solvent effects on the electronic and photophysical parameters of the three different substituted indium(III) phthalocyanines (4–6) are also reported. The humidity detection capabilities of the 4–6 films have also been investigated. Comparing humidity-sensing properties of the Pcs, it was found that the humidity sensitivity of 4 is higher than 5 and 6.

Synthesis, photophysics, and photochemistry of peripherally Schiff base-zinc complex substituted zinc phthalocyanine

Abstract The content of this work is based on the introduction of the salicylhydrazone-zinc complexes into the phthalocyanine core. The reaction of the salicylhydrazone substituted ZnPc (1) with the related zinc(II) salt in basic conditions in DMF yielded bis[bis(salicyhydrazone)phenoxy)zinc(II)] phthalocyaninato zinc(II) (5) in which two salicylhydrazone-Zn complexes are linked through oxygen bridges to the macrocyclic core as three-nuclear complex. The novel compound synthesized in this study was fully characterized by general spectroscopic techniques such as FT-IR, UV-vis, 1H NMR, 13C NMR, elemental analysis and mass spectroscopy. In addition, spectral, photophysical (fluorescence quantum yields), and photochemical (generation of singlet oxygen and photo stability under light irradiation) properties of newly synthesized phthalocyanine (5) and the starting Pcs molecules used to obtain this molecule were investigated in DMSO solutions, comparatively.

Synthesis, characterization and electrochemical properties of new phthalocyanines

Abstract The chemical synthesis and characterization with spectroscopic and electrochemical properties of [bis(4-fluorophenyl)-methoxy]-substituted metallo-phthalocyanines were reported for the first time. The new phthalocyanines have been characterized by elemental analysis, UV-Vis, FT-IR, and mass spectroscopies. The aggregation behavior of the phthalocyanine compounds was investigated in different solvents and concentrations. It is found that the fluoro substituents of peripherally Co and Cu complexes are examined and induce a shift to the redox processes toward the negative potentials and formed more reversible processes. Metal-based reduction and oxidation reactions were obtained for the Co(II) complex, whereas Cu(II) complexes exhibited Pc-ring-based electron-transfer reactions. The voltammetric measurements supported the proposed structure of the complexes.