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Journal of Porphyrins and PhthalocyaninesJ. Porphyrins Phthalocyanines 2020; 24: 499–601

See Yoshitaka Saga* and Shiori Nakagawa

pp. 499–504

The C132-S-epimers of chlorophyll (Chl) and bacteriochlorophyll (BChl) pigments play key roles in photosynthetic reaction center complexes although they are rarely present in photosynthetic organisms. The epimerization mechanism of (B)Chl pigments in vivo has not been unraveled. The structural effects on the physico-chemical properties of (B)Chl epimerization reactions provide useful information to tackle this question. This study clearly indicates that the bacteriochlorin skeleton retards the epimerization kinetics. Thus, BChl a exhibits slower epimerization kinetics than Chl a in spite of the presence of the electron-withdrawing 3-acetyl group that accelerates epimerization.

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Articles

pp. 505–514Self-assembly of amphiphilic meso-aryl-substituted porphyrin derivatives in the presence of surfactantsMargaret A. Gradova*, Oleg V. Gradov, Kseniya A. Zhdanova, Natalya A. Bragina and Anton V. Lobanov

This paper describes the synthesis of a number of new amphiphilic porphyrin derivatives and compares their aggregation behavior in aqueous media in the presence of different surfactants. The studies reveal the relationships between the molecular structure of the photosensitizer (particularly, the number and posi-tion of the peripheral alkyl chains) and the predominant type of intermolecular interactions realized in surfactant solutions at different pH both in micellar and submicellar concentration ranges.

pp. 499–504Structural effects on epimerization of bacteriochlorophyll a and chlorophyll a revealed using 3-acetyl chlorophyll aYoshitaka Saga* and Shiori Nakagawa

Epimerization of three pigments, BChl a, Chl a, and 3-acetyl Chl a, is compared to elucidate the structural factors that are responsible for the epimerization reactions. The current analyses clearly indicate that the bacteriochlorin skeleton retards the epimerization kinetics. Thus, BChl a exhibits slower epimerization kinetics than Chl a in spite of the presence of the electron-withdrawing 3-acetyl group that accelerates epimerization.

CONTENTS

J. Porphyrins Phthalocyanines 2020; 24: 499–601

pp. 515–527π-Electron delocalization and electronic transitions in oligomeric and polymeric phthalocyanine zinc(II) complexes. Part 1: Linear oligo- and one-dimensional polyphthalocyaninesSergei G. Makarov*, Günter Schnurpfeil, Sergey Yu. Ketkov and Dieter Wöhrle*

In this Part 1, linear oligomeric phthalocyanine zinc(II) with fused phthalocyanine macrocycles are described. By semi-empirical and DFT methods, UV-vis/NIR spectra, difference densities and energy gaps are evaluated. The optical gaps of oligophthalocyanines are compared with those of analogous oligoacenes. The optical gaps of the linear oligophthalocyanines are extrapolated to estimate the energy gap of 1D linear polyphthalocyanine, and the result is compared to the DFT calculation of the periodic structure with a plane-wave basis set.

pp. 528–537Preparative-scale purification of petroleum vanadyl porphyrins by sulfuric acid loaded macroporous silicaNikolay Mironov*, Dmitry Milordov, Guzalia Abilova, Elvira Tazeeva, Svetlana Yakubova and Makhmut Yakubov

Sulfuric acid soaked silica acts as a highly selective solid phase extraction agent in petroporphyrin purification. This property appears in a narrow range of water and sulfuric acid content in silica. Unprecedentedly simple preparation makes the silica-based sulfocationite suitable for preparative-scale purification of petroporphyrins.

pp. 548–562Octa-substituted metallophthalocyanines bearing (2,3- dihydrobenzo-1,4-benzodioxin-2-yl)methoxy and chloro groups: Synthesis, characterization and photophysico-chemical studiesSemih Gorduk*

Octa-substituted Zn(II), In(III) and Mg(II) phthalocyanines bearing (2,3-dihy-drobenzo-1,4-benzodioxin-2-yl)methoxy and chloro groups were synthesized and characterized. The effects of zinc, indium and magnesium metals, octa- substitution at peripheral positions and different types of solvents on photo- physicochemical properties were investigated.

pp. 538–547Synthesis of donor-π-acceptor porphyrins for DSSC: DFT-study, comparison of anchoring mode and effectivenessArtem V. Ezhov*, Fedor Yu. Vyal’ba, Kseniya A. Zhdanova, Andrey P. Zhdanov, Konstantin Yu. Zhizhin, Ilya N. Kluykin, Natal’ya A. Bragina and Andrey F. Mironov

Four porphyrin zinc complexes were synthesized as sensitizers for DSSC. Spectral characteristics and quantum chemical calculations based on DFT are presented, and the parameters of test solar cells were measured. A maximum efficiency of 4.33% was achieved using the dye ZnP4.

J. Porphyrins Phthalocyanines 2020; 24: 499–601

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pp. 577–588Amino acid adsorption on tetraphenyl porphyrin filmsJesus M. Rivera and Margarita Rivera*

Tetraphenylporphyrin films can be employed as amino acid selective detectors. Positively charged amino acids are more easily adsorbed on porphyrin films in contrast with polar molecules. Adsorption isotherms agree with morphological results regarding the formation of multilayers in all cases.

pp. 589–601Optical limiting properties, structure and simplified TD-DFT calculations of scandium tetra-15-crown-5 phthalocyaninatesAviwe May, Poulomi Majumdar, Alexander G. Martynov*, Lyudmila A. Lapkina, Sergey I. Troyanov, Yulia G. Gorbunova, Aslan Yu. Tsivadze, John Mack* and Tebello Nyokong

The optical limiting properties of the crown-ether-substituted scandium(III) phtha-locyanine complexes, bis-tetra-15-crown-5 phthalocyaninates Sc[(15C5)4Pc]2

•0 and Sc[(15C5)4Pc]2

-, together with monophthalocyaninate [(15C5)4Pc]Sc(OAc) were mea-sured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns). The crystal structure of the double decker Sc(III) complex was elucidated by means of single-crystal X-ray diffraction analysis and used to guide a series of theoretical calculations. It was demonstrated that the application of simplified time-dependent density functional theory (sTD-DFT) calculations can provide reasonably accurate predictions for compounds of this type when the geometries of the complexes are clearly defined.

pp. 563–576Discotic liquid crystals of transition metal complexes. 57: X-ray diffraction halo jumps originated from sudden free rotation of substituent groups to induce mesomorphismTakahiro Nishiguchi, Kouki Sugiyama, Hiromu Nakamura, Mikio Yasutake and Kazuchika Ohta*

From the fine measurements of halo positions at various temperatures by using the temperature-variable small angle X-ray diffraction technique, we have estab-lished for the first time that liquid-crystalline phases are induced by sudden free rotation of bulky groups and long alkyl chain groups, which appeared as X-ray diffraction halo jumps: [A] from 5.6 Å to 5.8 Å and [B] from 4.2 Å to 4.6 Å.