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Journal of Porphyrins and PhthalocyaninesJ. Porphyrins Phthalocyanines 2014; 18: 843–1062

Guest Editors: M. Salomé Rodríguez-Morgade, Tomás Torres and Atsuhiro Osuka

This issue of JPP is the second of two special issues dedicated to Professor Nagao Kobayashi on the occasion of his 65th birthday. They consist of 51 review and original research papers presented by his colleagues and friends, covering general topics on porphyrins, phthalocyanines and related macrocycles. Professor Kobayashi is a very ingenious scientist. His continual creativity has brought about a number of p orphyrin va riants with original structures and unusual properties. The cover picture shows the structures of some selected macrocycles that were designed and character-ized by Pro fes sor Kobayashi. These architectures display an assortment of shapes and sizes, as it can be found in edifices of Sendai, the city where he has developed his scientific career. Professor Kobayashi has also studied in depth properties such as chirality, absorption profiles and electronic structure of porphyrinoids. The cover background represents the ma gnetic circular dichroism spectroscopy (MCD), which is one of his areas of expertise.

About the Cover

Articles

pp. 849–855Synthesis and electronic properties of acetylene- and butadiyne-linked 3,3′-porphycene dimersTakuya Okabe, Daiki Kuzuhara*, Naoki Aratani and Hiroko Yamada*

The butadiyne- and acetylene-linked 3,3′-porphycene dimers 1 and 2 were synthesized from the common intermediate, 3-ethynyl-2,7,12,17-tetra-hexylporphycene 4. Crystal structure of 1 showed a coplanar structure of two porphyrin units. The optical and electrochemical measurements indicated weak interaction between the porphycene units through the linkage at 3,3′-positions.

pp. 843–848Supramolecular complex formation of resorcin[4]arene-modified zinc phthalocyanine and fullereneHitomi Momose, Hiroyuki Suzuki and Mutsumi Kimura*

A resorcin[4]arene-strapped zinc phthalocyanine 1, in which two benzene rings of the upper rim of resorcin[4]arene were fused to the adjacent phthalocyanine ligand, can capture C60 through the non-covalent interactions, and the comple x- ation between 1 and C60 results in an efficient photo-induced electron transfer.

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J. Porphyrins Phthalocyanines 2014; 18: 843–1062

pp. 856–868Discotic liquid crystals of transition metal complexes 51: Synthesis and mesomorphism of flat-pumpkin-shaped phthalocyanine-fullerene dyadsMiho Yoshioka, Kazuchika Ohta*, Yohei Miwa, Shoichi Kutsumizu and Mikio Yasutake

The authors have synthesized a novel type of donor–acceptor liquid crystalline material, phthalocyanine-fullerene (Pc-C60) dyad, [m, p, m′-(C14O)3PhO]6 PcCu-C60 (7). The flat-pumpkin-shaped Pc-C60 dyad 7 shows a Colho mesophase with a very big stacking distance of ca. 9.1 Å.

pp. 869–874Synthesis and properties of palladium(II) complexes of aromatic hemiporphyrazinesAtsuya Muranaka*, Fumiko Kyotani, Xingmei Ouyang, Daisuke Hashizume and Masanobu Uchiyama*

Palladium(II) complexes of aromatic hemiporphyrazines were prepared by the reaction of bis(dibenzylideneacetone)-palladium(0) with the corresponding metal-free macrocycles. Structural and electronic properties were studied by X-ray crystallography, NMR, UV-vis-NIR, and MCD spectroscopy.

pp. 875–883Phosphorus(V) tetrapyrazinocorrolazines — first cor ro lazine derivatives with fused heterocyclic ringsSvetlana S. Ivanova, Yulia Moryganova, Mahmoud Hamdoush, Oscar I. Koifman, Denis S. Sal’nikov and Pavel A. Stuzhin*

Tetrapyrazinocorrolazines — first corrolazine derivatives with annu-lated heterocycles — have been prepared as oxophosphorus(V) and dimethoxyphosphorus(V) complexes of octaphenyl substituted tetra-pyrazinocorrolazine and their UV-vis spectral and basic were studied in comparison to phosphorus(V) complex of octaphenylcorrolazine.

pp. 884–890Preparation of phthalocyanines fused with four tetrathiafulvalene units via the functional group transformation of tetrakis(o-xylylenedithio)phtha-lo cyanines with toluene/aluminum chlorideTakeshi Kimura*, Tadafumi Chiba and Shiduko Nakajo

Tetrakis(o-xylylenedithio)phthalocyanine and its nickel complex were treated with aluminum chloride in toluene and then with carbonyldi-imidazole to produce phthalocyanines with four 1,3-dithiole-2-one rings, respectively. The condensation of the nickel derivative with ethylenedithio-1,3-dithiole-2-thiones gave phthalocyanine having four ethylenedithiotetrathiafulvalene units.

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J. Porphyrins Phthalocyanines 2014; 18: 843–1062

pp. 891–898Meso-dichlorophenyl substituted Co(III) corrole: A se lec tive electrocatalyst for the two-electron reduction of dioxygen in acid media, X-ray crystal structure ana lysis and electrochemistryJijun Tang, Zhongping Ou*, Lina Ye, Minzhu Yuan, Yuanyuan Fang, Zhaoli Xue and Karl M. Kadish*

A cobalt corrole containing Cl substituents on the ortho-positions of three meso-phenyl rings was synthesized and structurely characterized. The electrochemis try was elucidated in three nonaqueous solvents and the electrocatalytic acti vi ty of the compound for reduction of dioxygen was also evaluated by cyclic voltam-metry and linear sweep voltammetry using a rotating disk electrode and a rotating ring-disk electrode.

pp. 899–908Asymmetric zinc phthalocyanines substituted with a single carboxyl and triethyleneoxysulfonyl groups: synthesis, characterization and validation for photo dynamic therapyDuygu Aydın Tekdaş, Ayşe G. Gürek* and Vefa Ahsen

In this study, the mono carboxyl acid substituted derivative of phthalo-cyanines were synthesized, and the photophysical and photochemical applications were investigated. Good singlet oxygen quantum yields of both complexes in DMSO ensure the potential candidates as the photo-sensitizer for PDT.

pp. 909–918N-confused phlorin: a stable dihydroporphyrin isomer containing a confused pyrrole ringMasatoshi Ishida, Kensuke Nakahara, Ryuichi Sakashita, Tomoya Ishizuka, Motonori Watanabe, Hidemitsu Uno, Atsuhiro Osuka and Hiroyuki Furuta*

Synthesis of bona fide N-confused phlorin derivatives through simple chemi-cal reduction of N-confused porphyrin precursors is described. Spectroscopic, X-ray diffraction analyses and DFT-assisted calculations support the nonaro-matic phlorin electronic structure.

pp. 919–932Asymmetry of chlorophylls in photosynthetic proteins: from the viewpoint of coordination chemistryToru Oba* and Hitoshi Tamiaki

Meta-analysis of crystallographic data of photosynthetic pigment-protein complexes was done from the viewpoint of coordination chemistry of (bac-terio)chlorophylls. It is noted that the cofactor pigments aggregated even in the proteins, and coordination chemistry of (B)Chls reflected the conditions enabling the aggregated states.

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J. Porphyrins Phthalocyanines 2014; 18: 843–1062

pp. 933–936Magnetic anisotropy and interaction between f-elec tronic systems in dinuclear inverted-sandwich-type lanthanide-phthalocyanine complexesSatoshi Tsuchiya, Akira Fuyuhiro, Takamitsu Fukuda and Naoto Ishikawa*

Dinuclear “inverted-sandwich-type” phthalocyanine complex with two terbium ions or dysprosium ions coordinated by two b-diketonato ligands have been found to have easy-plane magnetic anisotropy and antiferromagnetic f–f interac-tion. These results are completely opposite to those observed for corresponding Pc triple-decker complexes, which are known to function as single molecule magnets (SMMs).

pp. 937–943Aerobic oxidative N-dealkylation of secondary amines in aqueous solution catalyzed by rhodium porphyrinsLin Yun, Ling Zhen, Zikuan Wang and Xuefeng Fu*

Catalytic oxidative N-dealkylation of secondary amines was achieved using rhodium(III) tetra-(p-sulfonato-phenyl)porphyrin ((TSPP)RhIII) in aqueous solution with oxygen as the sole oxidant. Addition of benzalde-hyde to trap primary amine product inhibited catalyst deactivation and dramatically increased reaction turnover numbers (TONs). The reaction covered a decent range of aliphatic secondary amines and anilines. Kinetic and Hammett study suggest iminium ion as the intermediate of the rate determining step.

pp. 944–949Liquid crystalline properties of unsymmetrically subs-tituted phthalocyanines: structural features leading to nematic mesophase materialsAndrew D. Garland, Geoffrey C. Bryant, Isabelle Chambrier, Andrew N. Cammidge* and Michael J. Cook*

Nematic mesophase formation is only rarely observed, especially among phtha-locyanine based discogens. Here the phase is induced in non-peripherally substituted phthalocyanines by introduction of a hydrophilic hydroxyl group at the terminus of a single side-chain of appropriate length. The nematic mesophase is formed ex-clusively when the linking chain is significantly longer than the natural separation between cores in the columnar arrangement of pentyl-substituted phthalocyanines.

pp. 950–959β-conjugation of gadolinium(III) DOTA complexes to zinc(II) porpholactol as potential multimodal imaging contrast agentsXian-Sheng Ke, Juan Tang, Zi-Shu Yang and Jun-Long Zhang*

Synthesis of two bimodal imaging agents consist of a hydrophobic zinc(II) tetra-pentafluorophenylporpholactol core and a b-substituted hydrophilic Gd(III) DO3A (ZnLGd539) or DOTA (ZnLGd595) moiety has been described. Through b-conjugation approach, the absorption at deep red region increases compared to tradi tional conjuga-tion methods at meso-position. Combining the optical and ma gne tic resonance mea-surements in aqueous media, the observed largely enhanced r1 relaxivities was attri-buted to the aggregation of ZnLGd539 and ZnLGd595 in aqueous media. Furthermore, fluorescence and magnetic resonance imaging experiment showed that both ZnLGd539 and ZnLGd595 can be applied as potential bimodal imaging contrast agents and both compounds showed no dark cytotoxicity and good photocytotoxicity on Hela cells.

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J. Porphyrins Phthalocyanines 2014; 18: 843–1062

pp. 960–966Synthesis and in vitro study of new highly boronated phthalocyanineAkim V. Shmal’ko, Anastasija V. Efremenko, Anastasija A. Ignatova, Igor B. Sivaev*, Alexey V. Feofanov, Esin Hamuryudan, Ahmet Gül, Leonid V. Kovalenko, Shicheng Qi and Vladimir I. Bregadze

New highly boronated Zn(II)-phthalocyanine containing eight cobalt bis(dicarbollide) units (144 boron atoms) was prepared and its intracellular accumulation and distribution in GL6 human glioblastoma cells were studied.

pp. 967–974Synthesis, characterization and electrochemical pro per ties of meso-thiocarboxylate-substituted por phyrin deri vativesLeandro M.O. Lourenço, João Resende, Bernardo A. Iglesias, Kelly Castro, Shirley Nakagaki, Mário J. Lima, António F. da Cunha, Maria G.P.M.S. Neves, José A.S. Cavaleiro and João P.C. Tomé*

Bearing in mind the versatility of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPPF20) to react with nucleophiles, the authors highlight here the synthesis and cha racterization of several mono- and tetra-thiocarboxylate TPPF20 derivatives. It is emphasized their optical and electrochemical properties to evaluate the efficiency of fundamental electron transfer steps for dye sensitized solar cells (DSSCs).

pp. 975–981Alternative synthetic route toward octaiso propyl-porphyrins and structural deformation caused by a meso-butyl groupShun Sugawara, Takanari Kakui and Yohsuke Yamamoto*

Alternative synthetic route toward octaisopropylporphyrin (OiPPH2) and their metal complexes was developed. The X-ray structural analysis revealed that in-troduction of a butyl group at the meso-position in the complex induced different structural deformations determined by the central metal.

pp. 982–990Photoelectrochemical properties of supramolecular composites of an anionic zinc chlorin and Li+@C60 on SnO2Kei Ohkubo*, Yuki Kawashima, Kentaro Mase, Hayato Sakai, Taku Hasobe* and Shunichi Fukuzumi*

A photoelectrochemical solar cell composed of supramolecular nanoclusters of an anionic zinc chlorin and lithium-ion-encapsulated fullerene exhibits signifi-cant enhancement in the photoelectrochemical performance as compared with the reference system containing only a single component.

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J. Porphyrins Phthalocyanines 2014; 18: 843–1062

pp. 991–997Synthesis of phthalocyanine dimers and trimers connected via a nitrogen atom and amino phenyl groupsHasrat Ali and Johan E. van Lier*

The preparation of a variety of covalently linked Pc–Pc homo-dimers (ortho and meta), heterodimers and Pc–Pc triads linked through NH and bridged via N-aryl (phenyl) groups are reported.

pp. 998–1013Soluble meso-tetrakis(arylethynyl)porphyrins — syn thesis and optical propertiesAgnieszka Nowak-Król, Łukasz G. Łukasiewicz, Joy E. Haley, Mikhail Drobizhev, Aleksander Rebane*, Thomas M. Cooper* and Daniel T. Gryko*

Trans-A2B2-tetrakis(arylethynyl)porphyrin possessing good solubility was synthesized for the first time. It has significantly longer lifetime of T1 state (~450 μs) and enhanced two-photon absorption cross-section (500 GM) when compared with bis(arylethynyl)porphyrins and in their case all the states are mixtures of transitions between the HOMO-1, HOMO and LUMO, LUMO+1 MOs.

pp. 1014–1020Synthesis and spectroscopic properties of chiral bornane[2,3-b]pyrazino-fused [30]tri thia-do deca aza hexa phyrinsMaksim S. Filatov, Olga N. Trukhina*, M. Salomé Rodríguez-Morgade, Mikhail K. Islyaikin*, Oscar I. Koifman and Tomas Torres*

First chiral bornane[2,3-b]pyrazino-fused [30]trithiadodecaazahexa-phyrins were prepared by a crossover condensation of R-(+)- or S-(–)-bornane[2′,3′-b]-2,3-dicyanopyrazine and 2,5-diamino-1,3,4-thiadia-zole using two different methods. R-(+)- and S-(–)-enantiomers were characterized by measuring their optical rotations and circular dichroism spec-tra, showing a mirror image relationship with respect to [q] = 0. Regioisomers with C1 and C3 symmetry of R-(+)-[30]trithiadodecaazahexaphyrin have been separated using HPLC CHIRALPACK IC analytical column, allowing their unambiguous identification and characterization.

pp. 1021–1033Synthesis, spectroscopic, and cellular pro-per ties of α-pegylated cis-A2B2- and A3B-types ZnPcsBenson G. Ongarora, Zehua Zhou, Elizabeth A. Okoth, Igor Kolesnichenko, Kevin M. Smith and M. Graça H. Vicente*

Pegylated cis-A2B2- and A3B-type ZnPcs were synthesized and their spectroscopic and in vitro properties investigated in human HEp2 cells. These a-substituted ZnPcs were highly phototoxic, in particu-lar the amino-ZnPc.

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J. Porphyrins Phthalocyanines 2014; 18: 843–1062

pp. 1034–1041Synthesis and optical properties of trifluoroethoxy-subs tituted double-decker phthalocyaninesSatoru Mori, Naoya Ogawa, Etsuko Tokunaga and Norio Shibata*

The synthesis of trifluoroethoxy-substituted double-decker phthalocyanines was investi-gated for the first time. Phthalonitriles, including one trifluoroethoxy substituent at the a- or b-position, were nicely induced to double-decker phthalocyanines. Phthalonitrile having two trifluoroethoxy substituents at a-positions did not react, although the authors succeeded in leading b-di-substituted phthalonitrile to double-decker phthalocyanines.

pp. 1042–1050Zinc(II) complexes of tetrakis-(6,7-quinoxalino)por-phyrazine bearing externally appended 2-pyridyl rings: Synthesis, UV-visible spectral be ha vior and photo activity for singlet oxygen ge ne rationMaria Pia Donzello*, Giorgia De Mori, Elisa Viola*, Claudio Ercolani and Giampaolo Ricciardi

UV-visible spectral data in low polar solvents (pyridine, DMSO, DMF) of the new “quinoxalinoporphyrazine” macrocycles, the free base [Py8QxPzH2] and the Zn

II species [Py8QxPzZn], the respective octa-cation (neutralized by I- ions) and the ZnII/PdII pentanuclear complex [(PdCl2)4Py8QxPzZn], indicate a remarkable bathochromic shift of the Q(0,0) band relative to the pyrazinoporphyrazine analogs, a feature that can be explained on the basis of recent DFT/TDDFT studies on the related couple of analogous MgII complexes.

pp. 1051–1056Some observations regarding the behavior of boron subphthalocyanines in polar aprotic solventsAndrew S. Paton and Timothy P. Bender*

In this paper, some observations from the attempted reaction of Br-BsubPc with phenol in DMF and DMAc is described. During these efforts, it was found that Br-BsubPc reacts with the respective solvents to produce axially substituted formate-BsubPc and acetate-BsubPc.

pp. 1057–1062Catalysis by substituted iron phthalocyanines of crystal violet leucobase oxidation with dioxygenTatiana M. Fedorova*, Valentina M. Derkacheva, Eugene A. Lukyanets and Oleg L. Kaliya

The catalytic reaction of crystal violet leucobase oxidation by dioxygen in o-dichlorobenzene with formation of corresponding dye was studied with using substituted iron phthalocyanines as the catalysts.

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