Supramolecular assemblies of pyridyl porphyrin and diazadithia phthalocyanine

In this paper we report for the first time on a mixed complex between the cationic porphyrin 5, 10, 15, 20-tetra-N- -methyl-pyrydinium-p-il porphyrin (TMPyP) and a new metal phthalocyanine with four 16-membered diazadithia macrocycles (denoted here as Pc16), in order to obtain an active complex with an intense absorption on the lower energy side of the visible spectrum and with a higher sensitivity in photodynamic therapy of cancer. The dimerization constant for Pc16 and also the ratio between the oscillator strengths for monomeric and dimeric forms of this compound, were evaluated. The ratio between these oscillator strengths was 2.01 showing a certain dimerization process. The Job mathematical method allowed the establishment of the stoichiometry and the formation constants for the heteroaggregates between the porphyrin and the phthalocy- anine (a diad between one phthalocyanine molecule and one porphyrin molecule and a triad between two phthalocyanine molecules and only one porphyrin molecule). The coulombic attraction resulting from the p-p interaction of the two highly conjugated macrocycles and from the interaction between the substituents, favors a face-to-face geometry

Synthesis, characterization, DFT study, conductivity and effects of humidity on CO2 sensing properties of the novel tetrakis- [2-(dibenzylamino)ethoxyl] substituted metallophthalocyanines

Acar-Selcuki, Nursel/0000-0001-9292-0637; senoglu, sema/0000-0002-1618-6570; Ozer, Metin/0000-0002-1173-2405WOS: 000519306300053Novel tetrakis[2-(dibenzylamino)ethoxyll substituted nickel (II), cobalt (II) and manganese (II) phthalocyanines were synthesized by using 4-(2-(dibenzylamino)ethoxy)phthalonitrile with corresponding metal salts in 2-N, N-dimethylaminoethanol. New phthalonitrile ligand was prepared from 2-(dibenzylamino)ethan-l-ol and 4-nitrophthalonitrile in acetonitrile at reflux temperature using potassium carbonate as catalyst. the compounds was characterized by elemental analysis, infrared, ultraviolet-visible and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopic methods. Density functional theory calculations were performed for structural and electronic properties. Direct current and alternating current conductivity properties of the metallophthalocyanine films were investigated between 293 - 523 K and frequencies 40 -100 kHz. the direct current conductivity values were calculated as 5.29 x 10(-10 )S/cm, 2.39 x 10(-9)S/cm, and 3.04 x 10(-10) S/cm, for nickel, cobalt and manganese complexes (293 K) films, respectively. Activation energies of the films were 0.50-0.70 eV for T < 478 K. Alternating current conductivity results suggest that hopping model explains dominant charge transport mechanisms. Carbon dioxide sensing properties (1000-8000 ppm) of the metallophthalocyanine films were investigated at room temperature (293 K) in air as background. Additionally, effects of the relative humidity on carbon dioxide sensing properties were also investigated for relative humidity between 0-80 % RH in air. Response and response time values of the films were reported. Newly synthesized phthalocyanine complexes in this study were found to be reversible and sensitive to the carbon dioxide gas in humid air. Carbon dioxide sensing measurements revealed that sensitivity of the sensors increased with increasing carbon dioxide concentration and relative humidity. It is found that manganese phthalocyanine showed greater sensitivity than nickel- and cobalt phthalocyanine complexes.Ministry of Development-Republic of TurkeyTurkiye Cumhuriyeti Kalkinma Bakanligi [2016 K121230]; Turkish Academy of Science (TUBA)Turkish Academy of Sciences; Marmara University Scientific Research CommitteeMarmara University [FEN-CYLP-120917-0552, FEN-D-120418-0176, FEN-BGS-290506-0114]This work was supported by Ministry of Development-Republic of Turkey with the project Number: 2016 K121230. Ozer Bekaroglu and Bekir Salih gratefully acknowledge the Turkish Academy of Science (TUBA) for the partial financial support. Authors also thank to Marmara University Scientific Research Committee (Project Numbers: FEN-CYLP-120917-0552, FEN-D-120418-0176 and FEN-BGS-290506-0114) for their support. the authors are grateful to the TUBITAK-ULAKBIM Truba Resources for computer time

Synthesis of phthalocyanines crosswise-substituted with two alkylsulfanyl and two crown-ether

1236-1238Crosswise-substutited phthalocyanines with two nitro and two dodecylsulfanyl groups are synthesized by a 1:1 condensation of 1,3-dihydro-1,3-diimino-6-(n-dodecylsulfanyl) isoimino indolenine with 6-nitro-1,3,3-trichloroisoindolenine in the presence of sodium methoxide, hydroquinone and triethylamine. Nitro substituents are reduced to amines by sodium sulfide and condensation of the amino groups with benzo-15-crown-5-aldehyde results in a new Pc with two benzo-15-crown-5-imino substituents. The compounds have been characterized by elemental analyses, UV/Vis and IR spectroscopy. </span

Synthesis, characterization, third-order non-linear optical properties and DFT studies of novel SUBO bridged ball-type metallophthalocyanines

Acar-Selcuki, Nursel/0000-0001-9292-0637; alizadeh, shabnam/0000-0003-3601-807X; Salih, Bekir/0000-0002-8542-6531; Ozer, Metin/0000-0002-1173-2405; Gork, Gulsen/0000-0003-3947-6332WOS:000599093600024PubMed: 33201973Novel 4,4 '-(((2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis(2-methylpropane-2,1-diyl))bis(oxy)) (SUBO) bridged ball-type metallophthalocyanines were synthesized starting from 4,4 '-(((2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis(2-methylpropane-2,1-diyl))bis(oxy))diphthalonitrile with convenient metal salts in 2-N,N-dimethylaminoethanol. A new bisphthalonitrile compound was obtained from 2,2 '-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis(2-methylpropan-1-ol) and 4-nitrophthalonitrile in acetonitrile at reflux temperature in the presence of potassium carbonate as a catalyst. The structural characterization of the compounds was performed by elemental analysis, and infrared, ultraviolet-visible and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopic methods. Nonlinear absorptions of the phthalocyanine complexes were measured using the Z-scan technique with 7 ns pulse duration at a 532 nm wavelength. It is obvious that ball-type copperphthalocyanine has a high nonlinear absorption coefficient and imaginary component of the third-order susceptibility compared to other complexes. Therefore, ball-type copperphthalocyanine can be regarded as a very good candidate for optical limiting applications. Density functional theory was used for geometry optimizations and time-dependent density functional theory calculations of electronic transitions in order to compare with the experimental results. Molecular orbital and nonlinear optical analyses were also performed with density functional theory at the CAM-B3LYP/6-31G(d,p)/LANL2DZ level. The nonlinear optical analyses show that ball-type copperphthalocyanine has significantly better nonlinear optical properties in comparison to a common reference compound, urea.Ministry of Development-Republic of TurkeyTurkiye Cumhuriyeti Kalkinma Bakanligi [2016 K121230]; Turkish Academy of Science (TUBA)Turkish Academy of Sciences; Marmara University Scientific Research Project Coordination Unit (BAPKO)Marmara University [FEN-B-101018-0525]This work was supported by the Ministry of Development-Republic of Turkey with the project Number: 2016 K121230. ozer Bekarolu and Bekir Salih gratefully acknowledge the Turkish Academy of Science (TUBA) for the partial financial support. This work was also supported by the Marmara University Scientific Research Project Coordination Unit (BAPKO) with the project number (FEN-B-101018-0525). Computer time provided by Fen Cluster (Ege University Faculty of Science) and TUBITAK ULAKBIM TRUBA Resources is gratefully acknowledged