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Journal of Porphyrins and PhthalocyaninesJ. Porphyrins Phthalocyanines 2020; 24: 1–497

pp. i

Guest editors: Tomás Torres, Jonathan L. Sessler, Dongho Kim and Hiroyuki Furuta

This issue of JPP is dedicated to Professor Atsuhiro Osuka on the occasion of his 65th birthday and formal retirement from Kyoto University. It consists of 55 reviews and original research papers presented by his colleagues and friends. The cover picture illustrates as a photographic mosaic a crystal structure gallery of porphyrinoid com-pounds reported by the Osuka group. The stitching making up the cover background is a picture of the Kiyomizu-Dera temple, an emblematic landmark of Kyoto, the city where Prof. Osuka developed his scientific carrier.

About the Cover

Reviews

pp. 1–2021-Carbaporphyrin: A cyclopentadiene moiety entrapped into a porphyrin scaffold Anna Berlicka* and Lechosław Latos-Grażyński*

Incorporation of a plain cyclopentadiene ring into the archetypal β- or meso-substituted porphyrin frames created two original groups of carbaporphyri-noids, β-substituted 21-carbaporphyrins and meso-tetraaryl-21-carbaporphy-rins. This review reports on the state of the art of 21-carbaporphyrin chemistry. The synthetic strategy, physicochemical characterization and some insight into coordination properties of 21-carbaporphyrins have been comprehensively exemplified.

pp. 21–32Photocatalytic redox reactions with metalloporphyrinsShunichi Fukuzumi*, Yong-Min Lee* and Wonwoo Nam*

Metalloporphyrinoids are utilized as efficient sensitizers and catalysts in photo-synthesis and the reverse reaction that is respiration. Metalloporphyrins act as photo redox catalysts with for hydrogen evolution and as thermal redox catalysts for photocatalytic reduction of CO2 with photoredox catalysts. Metalloporphyrins are also used as dual-function catalysts: as photoredox catalysts for oxygenation of substrates with H2O as an oxygen source and as redox catalysts for the reduction of O2 as a two-electron oxidant.

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J. Porphyrins Phthalocyanines 2020; 24: 1–497

pp. 33–42Polar columnar assemblies of subphthalocyaninesMaria J. Mayoral*, Tomás Torres* and David González-Rodríguez*

This small review highlights the ability of fluorosubphthalocyanines to self-assemble into columnar non-centrosymmetric nanostructures, thus generating novel polarly ordered liquid crystalline materials which, in the presence of electric fields, can be aligned to produce unprecedented switchable or permanently polarized materials.

pp. 67–74Effects of meso-diarylamino group of porphyrins on optical and electrochemical propertiesTomohiro Higashino, Yamato Fujimori, Issei Nishimura and Hiroshi Imahori*

We report the synthesis and optical and electrochemical properties of meso-diarylaminoporphyrins with multiple meso-diarylamino groups. Notably, the high electron-donating ability of the porphyrin with four meso-diaryl amino groups suggests the potential utility of multiply meso-aminated porphyrins as hole-transporting materials and as electron donors forming charge-transfer complexes.

pp. 75–83meso-Free dipyrrins: Formation of assembled structures including a 2D ordered pattern Atsuko Kuno, Kazuto Nakamura, Yoshihiro Kikkawa and Hiromitsu Maeda*

Fairly planar meso-unsubstituted dipyrrins, some of which had trialkoxyphenyl moieties, were synthesized. They underwent self-assembly in less polar solvents and exhibited a 2D ordered pattern at the solid/liquid interface, as observed through scanning tunneling microscopy.

Articles

pp. 43–66Porphyrin–diketopyrrolopyrrole conjugates and related structures: Synthesis, properties and applicationsVítor A. S. Almodôvar and Augusto C. Tomé*

The synthesis, properties and applications of porphyrin–diketopyrrolopyrrole conjugates and related structures with tetrabenzoporphyrin, bacteriochlorin, phthalocyanine, porphycene, calix[4]pyrrole or BODIPY units is reviewed.

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pp. 90–97Electrochemical properties and catalytic reactivity of cobalt complexes with redox-active meso-substituted porphycene ligandsTaro Koide, Zihan Zhou, Ning Xu, Yoshio Yano, Toshikazu Ono, Zhongli Luo, Hisashi Shimakoshi and Yoshio Hisaeda*

The cobalt complexes of meso-aryl-substituted porphycenes were synthesized and characterized. The reduction potentials of the complexes could be tuned by changing the meso-substituents, and the one-electron reduction of the complexes afforded the ligand-reduced radical anion species. The generated ligand-reduced species reacted with alkyl halides to form Co(III)-alkyl complexes. The catalytic reaction with trichloromethylbenzene was also performed, and it was found that the ratio of the obtained products was changed by the reduction potentials of the catalyst.

pp. 98–104Dithienothiophene fused 30p heptaphyrin and 34p octaphyrins: Syntheses, characterization and spectral propertiesSyamasrit Dash, Arindam Ghosh and Tavarekere K. Chandrashekar*

Aromatic singly fused 30π heptaphyrin and doubly fused 34π octaphyrins are reported. Protonation did not cause structural change in heptaphyrin while severe structural changes with inversion of rigid DTT moiety were observed in octaphyrin derivative.

pp. 84–89Synthesis and properties of 5-aza-15-thiaporphyrinsDaisuke Yamashita, Hiroto Omori, Norihito Fukui and Hiroshi Shinokubo*

We prepared 5-aza-15-thiaporphyrin through nucleophilic sulfination of nitrogen-bridged dibromobisdipyrrin. X-ray diffraction analysis elucidated its structure in the solid state. Due to its relatively distorted structure, 5-aza-15-thiaporphyrin shows weak antiaromaticity. The sulfur atom was oxidized to provide 5-aza-15-thiaporphyrin S-dioxide, which exhibited fluorescence in solution.

pp. 105–111Synthesis and electronic properties of meso-tetra(3,4,5-trimethoxy)phenyl-porphyrin and -tetrabenzoporphyrin and their phosphorus complexesTaniyuki Furuyama*, Yuichi Takahashi, Tomoteru Fukumura, Ana C. C. Bacilla and Nagao Kobayashi*

meso-Tetra(3,4,5-trimethoxyphenyl)-porphyrin and -tetrabenzoporphyrin and their phosphorus(V) complexes have been synthesized and spectroscopically character-ized. On P(V) ion-insertion, the intensity of the Soret band decreased significantly and concomitantly shifted to a longer wavelength, while the Q band of the benzo-porphyrin intensified significantly. Quantum chemical calculations have also been performed to enhance the interpretation of spectroscopic properties.

pp. 129–134The synthesis of a hexameric expanded hemi-porphyrazine Briana R. Schrage, Kullapa Chanawanno, Laura A. Crandall and Christopher J. Ziegler*

The field of expanded porphyrins is well developed. In contrast, expanded macrocycles such as phthalocyanines and hemiporphyrazines have been less explored. In this report we present the synthesis and characterization of a new hexameric expanded hemiporphyrazine which we refer to as hexahemi porphyrazine, which was characterized spectroscopically and by X-ray crystallography.

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pp. 112–120Heteroleptic palladium(II) complexes of dipyrrin-1,9-dione supported by intramolecular hydrogen bondingClayton J. Curtis and Elisa Tomat*

The dipyrrin-1,9-dione framework, which is characteristic of the propent dyopent family of heme metabolites, forms heteroleptic Pd(II) complexes featuring primary amine ligands. Within these planar complexes, the dipyrrindione motif combines reversible ligand-based redox chemistry with interligand hydrogen bonding in the primary coordination sphere of the metal center.

pp. 121–128Unsymmetrical bipyrrole derived highly soluble and emissive b-dialkylporphycenes with good singlet oxygen generation abilityNarendra N. Pati, B. Satish Kumar, Dharani Sivadasan, Sipra Sucharita Sahoo and Pradeepta K. Panda*

Novel β-dialkylated porphycenes, as their 2,12- and 2,17-substi-tuted analogues were realized for the first time in porphycene chemistry. This mode of unsymmetrical substitution was found to unexpectedly enhance the solubility of these porphycenes in common organic solvents. The positional effects of alkyl groups could be controlled through diversification in structures of the porphycene core. The crystal structure of 2,17-di-n-propylporphycene indicates presence of two molecules in the asymmetric unit with different orientation of the alkyl chains with respect to the macrocyclic core.

pp. 135–142Synthesis of nonplanar meso-trifluoromethyl-substituted tetrabenzoporphyrins via oxidation of tetrabutanoporphyrinsKoji Okinaga and Masaaki Suzuki*

Simultaneous synthesis of meso-trifluoromethyl-substituted tetrabutano-porphyrins, which have one or two trifluoromethyl groups at their 5-, 5,10-, and 5,15-positions, and the subsequent oxidation reactions into the corresponding meso-trifluoromethyl-substituted tetrabenzoporphyrins have been achieved.

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pp. 143–152Photoinduced electron transfer from zinc meso-tetraphenylporphyrin to a one-dimensional perylene diimide aggregate: Probing anion delocalization effectsJoaquin M. Alzola, Natalia E. Powers-Riggs, Nathan T. La Porte, Ryan M. Young*, Tobin J. Marks* and Michael R. Wasielewski*

We have investigated how the interactions of three perylenediimide acceptor chromophores affects the rate of photoinduced electron transfer from a zinc meso- tetraphenylporphyrin donor. Using transient visible and infrared absorption spectroscopy, we found that increasing the number of acceptors from two to three does not lead to an increase in the rate of charge separation. The orientation of acceptor chromophores in a rigid one-dimensional stack does not enable access to a lower energy state to further enhance electron transfer, due to weak coupling to the distal PDI.

pp. 171–180Acid–base controllable singlet oxygen generation in supramolecular porphyrin–gold nanoparticle composites tethered by rotaxane linkersAkira Shinohara, Chengjun Pan, Lei Wang and Hideyuki Shinmori*

A mechanically-interlocked photosensitizer–quencher system has been developed utilizing tetraphenylporphyrin (H2TPP)–gold nanoparticle (AuNP) composites tethered by rotaxane linkers. The H2TPP-substituted 24-crown-8 was able to shuttle along the alkanethiolate axle triggered by deprotonation/protonation at the ammonium station in the composite, causing the change in the H2TPP–AuNP distance and the photoexcited energy transfer efficiency.

pp. 153–1605,10,15-Triarylcorrole atropisomerismMartina Bischetti, Giuseppe Pomarico, Sara Nardis, Federica Mandoj, Daniel O. Cicero and Roberto Paolesse*

The restricted rotation of the meso-aryl rings about the macro cyclic plane has been investigated in 5,10,15-tris(2,5-disub stituted)phe-nylcorrole free bases, by means of different NMR techniques. The study gives insights on the kinetic and thermodynamic factors driving the atropisomerism in triarylcorrole derivatives.

pp. 161–170Tropylium cation-fused aromatic [26]dicarba-porphyrinoids with NIR absorptions: Synthesis, spectroscopic and theoretical characterizationKrushna C. Sahoo, Mohandas Sangeetha, Dandamudi Usharani* and Harapriya Rath*

The first-ever isolation and characterization of aromatic [26]dicarbaporphy- rinoids with NIR absorption being benefitted by tropylium character of the seven-membered rings is reported.

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J. Porphyrins Phthalocyanines 2020; 24: 1–497

pp. 181–190Alkylation, metalation and ring contraction of tropiporphyrinTimothy D. Lash* and John M. Rooney

Tropiporphyrin selectively reacted with methyl iodide and potassium carbonate to give a 24-methyl derivative. Subsequent reaction with Pd(OAc)2 afforded a palladium(II) com-plex that retained the N-methyl substituent. However, N-unsubstituted tropiporphyrin reacted with Pd(OAc)2 to give two palladium(II) benziporphyrins, albeit in low yields, one of which possessed a formyl substituent. Mechanisms are proposed to explain these unexpected ring contractions that involve Pd(II) addition and Cope rearrangements.

pp. 191–199meso-1,4-Phenylene-bridged nickel norcorrole dimerJi-Young Shin*

Nickel norcorrole (NiNC) dimer, linked by phenylene bridge was prepared by nickel-mediated homo-coupling of meso-phenylene bisdipyrrin nickel(II) dimer. The unique structure was elucidated by X-ray diffraction analysis and the structure distinctions between monomeric and dimeric NiNCs were established with vibration spectroscopic analysis and assessed with DFT calculations.

pp. 200–210Evaluation of covalently linked (bacterio)chlorin-fullerenes as components for organic solar cellsShin-ichi Sasaki*, Shengnan Duan, WeiDong Hu, Xiao-Feng Wang* and Hitoshi Tamiaki*

A series of covalently linked (bacterio)chlorin-fullerenes were synthesized and their application to organic photovoltaics was investigated. In the single material device, the conjugates consisting of chlorophyll donor and fullerene acceptor units were demonstrated to function as a photoactive layer. The power conversion efficiency of 0.62% was achieved without the use of an additional fullerene, which was requisite for bulk-heterojunction solar cells.

pp. 211–219Singlet oxygen generation of subphthalocyanine-fused dimer and trimerRei Fujishiro, Hayato Sonoyama, Yuki Ide, Takuya Fujimura, Ryo Sasai, Nichole E. M. Kaufman, Zehua Zhou, M. Graça H. Vicente and Takahisa Ikeue*

We obtained a chlorinated SubPc dimer and trimer which were combined in two SubPc rings, by introducing a common benzene ring. Subsequent research revealed that the SubPc dimer and trimer showed the potential to generate 1O2 not only in toluene but also in DMSO.

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pp. 220–2292,6-/1,5-Naphthoquinodimethane-bridged porphyrin dimer diradicaloids Hejian Zhang, Jinseok Kim, Hoa Phan, Tun Seng Herng, Tullimilli Y. Gopalakrishna, Wangdong Zeng, Jun Ding, Dongho Kim* and Jishan Wu*

Two porphyrin dimers with either 2,6-naphthoquinodimethane (for 2,6-P2) or 1,5-naphthoquinodimethane (for 1,5-P2) bridges were synthesized. Both com-pounds show open-shell singlet ground states. The 1,5-P2 isomer exhibited a larger diradical character and longer wavelength but weaker one-photon absorption, a smaller singlet-triplet energy gap, and a smaller two-photon absorption cross-section maximum compared with the 2,6-P2 isomer.

pp. 238–246Antiferromagnetic coupling in copper(II)porphyrin dimers linked by copper(II) or palladium(II) ionMary-Ambre Carvalho, Hervé Dekkiche, Sébastien Richeter, Corinne Bailly, Lydia Karmazin, Declan McKearney, Daniel B. Leznoff, Guillaume Rogez, Bertrand Vileno, Sylvie Choua* and Romain Ruppert*

The synthesis of porphyrin dimers linked by metal ions is described and the X-ray structure of two new dimers is presented. Antiferromagnetic coupling be-tween copper(II) porphyrins linked by copper(II) was demonstrated by EPR and SQUID measurements.

pp. 247–251Chiral carbazole-based porphyrins showing absorption and circular dichroism in the near-infrared regionChihiro Maeda* and Tadashi Ema*

Chiral carbazole-based porphyrins were synthesized for the first time via the incorporation of hydrobenzoin units at the thiophene moieties. They showed NIR absorption and circular dichroism, and a clear Cotton effect was observed in the NIR region.

pp. 230–237meso-(2-Benzimidazolyl)-substituted BODIPYs: Syn-thesis, structures and spectroscopic propertiesHu Gao, Chenhong Li and Zhen Shen*

We have synthesized and characterized a series of meso-(2-benz-imidazolyl) BODIPY derivatives. The absorption and fluorescence bands of 3a are centered at 533 and 578 nm, and its ΦF value is up to 0.45 in toluene which is much higher than those of previously reported meso-hetero cyclic BODIPYs. The distyryl coupled BODIPY 4 absorbs at 676 nm and emits at 712 nm along with ΦF value over 0.3 both in nonpolar and polar solvents, which suggests that meso-(2-benzimidazolyl) BODIPY can be used as a good platform for post modification to achieve NIR dyes for various applications in material and biological sciences.

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pp. 252–258Iron complex of a quadruply fused porphyrin: Synthesis, structure and redox propertiesTomoya Ishizuka*, Keiyu Komamura, Yuta Saegusa, Shogo Tanaka, Yoshihito Shiota, Kazunari Yoshizawa and Takahiko Kojima*

An iron(II) complex of a quadruply ring-fused porphyrin has been newly syn-thesized and characterized. The ESR spectrum of 1e--reduced Fe-1, formed by controlled-potential bulk electrolysis in pyridine, showed a signal at g = 2.003 with a well-resolved 45-line hyperfine splitting at room temperature, due to the coupling with four nitrogen and twelve hydrogen nuclei of the QFP ligand.

pp. 259–267Supramolecular dimerization of a hexameric hemo-protein via multiple pyrene–pyrene interactionsKoji Oohora*, Shota Hirayama, Tsuyoshi Mashima and Takashi Hayashi*

A supramolecular assembly of a hexameric hemoprotein modified with pyrene molecules was investigated. A maleimide-tethered pyrene molecule was reacted with a cysteine-introduced hexameric hemoprotein mutant. Multiple pyrene–pyrene interactions promote supramolecular dimerization of the modified hexamer. Interestingly, the assembly dissociates to the inherent hexamer upon removal of heme. Subsequent insertion of heme regenerates the dimer of the hexamers.

pp. 268–277Porphyrin-rylene-diimide-hexabenzocoronene triads Max M. Martin, Carolin Dusold, Andreas Hirsch* and Norbert Jux*

Triads consisting of porphyrin, hexa-peri-hexabenzocoronene and rylene building blocks were prepared and photophysically investigated. UV-vis absorption and fluorescence emission spectroscopy showed interesting pho-tophysical behavior such as energy transfer processes. Particularly, the porphyrin–perylene-HBC shows strong absorption features between 330–650 nm, which covers a wide range of the visible spectrum.

pp.278–285Synthesis and characterization of porphyrin–pyrene hybridsMin Liang, Yuanyuan Li, Mingbo Zhou*, Yutao Rao, Bangshao Yin, Ling Xu, Tingting Gu, Xu Liang, Weihua Zhu, Donghai Yu, Shubin Liu and Jianxin Song*

Palladium-catalyzed Suzuki–Miyaura coupling of 5-functionalized Ni(II) porphyrins with 1,3,6,8-tetra-functionalized pyrenes was carried out to obtain two kinds of porphyrin–pyrene hybrids. The structure of 4Zn, a porphyrin tetramer was determined by X-ray diffraction analysis, and the presence of energy transformation from pyrene moiety to porphyrin unit has been proved by emission spectra.

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pp. 286–297Synthesis and optical, magnetic, and electrochemical properties of 5,10,15,20-tetraaryl-5,15-diazaporphyrin–tertiary amine conjugatesKeisuke Sudoh, Yuna Satoh, Ko Furukawa, Haruyuki Nakano and Yoshihiro Matano*

This paper reports on the optical, magnetic, and electrochemical properties of nickel(II) and copper(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrin–tertiary amine conjugates which were prepared by metal-templated cyclization and redox reactions. The 18π derivatives exhibited charge-transfer bands in the near infrared region and underwent electrochemical polymerization on the electrode surface.

pp. 298–302Non-planar core-modified dibenzi expanded isophlorinRakesh Gaur, Madan D. Ambhore and Venkataramanarao G. Anand*

Ortho-phenylene-bridged dibenzi expanded iso- phlorin formally accounts as a 32π anti-aromatic macrocycle. It loses its planarity due to steric hindrance from the benzene units connected through its ortho carbons and hence adopts a unique V-shaped structure in the solid state. Similar to other known antiaromatic isophlorins, it undergoes two-electron ring oxidation, but it yields an unstable aromatic dicationc species.

pp. 303–313Ruffling and doming: Structural and redox studies on meso-aryl and b-alkyl chromyl(V)corrolesPeter Schweyen, Christian Kleeberg, Dominik Körner, Anne Thüsing, Richard Wicht, Marc-Kevin Zaretzke, Martin Bröring*

A series of chromyl(V) corroles with a meso-triaryl and β-octaalkyl substitution pattern is reported, and a conformational analysis of macrocycle distortion points to severe ruffling as a major mode.

pp. 314–319Extraction of carbon nanotubes with porphyrin- and pyrene-based nanotweezers and nanocalipers: Insight from the association constantsAlejandro López-Moreno*, Yujing Jiang, Guoqing Cheng and Naoki Komatsu*

We have been developing V- and U-shaped porphyrins and pyrenes, designated as nanotweezers and nanocalipers, respectively, for separation of carbon nano-tubes through their extraction to liquid phase. In this paper, we synthesized various host molecules including novel porphyrin-cored nanocalipers, and determined the association constants (logKassociation) of nanocalipers, nanotweezers, porphyrins, and pyrenes with single-walled carbon nanotubes to be around 5, 4, 3, and 1, respectively.

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pp. 320–329meso-Tetraphenylporphine as a prochiral solvating agent (pro-CSA): A physicochemical study Jan Labuta*, Shinsuke Ishihara and Jonathan P. Hill*

We present in-depth analysis of the enantiomeric excess (ee) sensing capability of achiral meso-tetraphenylporphine. The 2–phenoxypropionic acid serves as a model analyte of which the ee is determined. The analysis has been performed in broad range of conditions (temperatures and concentrations) departing markedly from optimum, thus revealing further effects and limitations connected with the pro–CSA sensing method. In this investigation variable temperature NMR, titration experiments and analyses of NMR spectral line shapes have been used.

pp. 330–339Synthesis and characterization of novel 5-monocar-bohydrate-10,20-bis-aryl-porphyrinsFlávio Figueira*, Leandro M. O. Lourenço, Maria G. P. M. S. Neves, José A. S. Cavaleiro and João P. C. Tomé*

This work discribes the preparation and characterization of bis-aryl-porphyrins bearing glucose or galactose units linked by an acrylate spacer to one free meso position.

pp. 340–349Design of metalloporphyrins fused to imidazolium rings for binding DNA G-quadruplexesFrancesca Caporaletti, Jenifer Rubio-Magnieto, Mamadou Lo, Jean-François Longevial, Clémence Rose, Sébastien Clément, Arie van der Lee, Mathieu Surin* and Sébastien Richeter*

Nickel(II) meso-tetraarylporphyrins fused to imidazolium rings across β,β-pyrrolic positions were synthesized and their interactions with DNA G-quadruplexes were investigated by UV-vis absorption spectroscopy, circular dichroism spectroscopy, and Fluorescence Resonance Energy Transfer (FRET) melting assay.

pp. 350–354Functionalized mesoporous silica nano- particles with 2,7,12,17-tetraphenylpor- phyceneGabriel Martínez-Edo, Maria LLinàs, Gonzalo Anguera, Albert Gibert and David Sánchez-García*

Mesoporous silica nanoparticles decorated with 2,7,12,17-tetraphenylporphycene have been prepared by reaction of aminated nanoparticles with 9-(glutaric N-succinimidylesteramide)-2,7,12,17-tetraphenylporphycene. The as-prepared nanoparticles were characterized by UV-vis spectroscopy, DLS and TEM.

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pp. 355–361Oxidative nitration reaction of anti-aromatic 5,15-dioxaporphyrinAkihide Nishiyama, Yuki Tanaka, Shigeki Mori, Hiroyuki Furuta* and Soji Shimizu*

Upon oxidation of 20π-electron antiaromatic 5,15-dioxapor-phyrin (DOP) using nitrosonium ions as oxidants, a tetrakis-β-nitrated compound was formed via an oxidative nitration reaction mechanism. Compared with the original DOP, this tetranitro DOP product exhibited a blue-shift of absorption and down-field shifts of the β-pyrrolic proton signals. The unique antiaromatic electronic structure of the tetranitro DOP was experimentally disclosed by electrochemistry and theoretically by DFT and NICS calculations.

pp. 362–378Bioconjugatable synthetic chlorins rendered water-soluble with three PEG-12 groups via click chemistryNobuyuki Matsumoto, Masahiko Taniguchi and Jonathan S. Lindsey*

A synthetic free base chlorin has attractive spectral features for a red-region fluorophore (λabs = 410 and 640 nm; λem = 644 nm; Φf = 0.19) in water.

pp. 379–385A Möbius-expanded porphyrinoid with 2,3-pyrrollic connection from a planar p-extended BODIPYAdiki Raja Sekhar and Jeyaraman Sankar*

Herein, the first example of a novel BF2-complex of an octaphyrin with Möbius topology has been revealed. A planar BODIPY precursor offered the macro-cycle on oxidative dimerization. An unprecedented 2,3-pyrrolic connectivity was observed for the meso-aryl substituted octaphyrin(1.0.0.0.1.0.0.0). X-ray diffraction, NMR studies and DFT calculations unambiguously support the Möbius topology.

pp. 386–393Quinoline-annulated porphyrin platinum complexes as NIR emittersJoshua Akhigbe, Michael Luciano, Adewole O. Atoyebi, Steffen Jockusch and Christian Brückner*

The Pt(II) complexes of the mono- and bis-quinoline-annulated porphyrins exhibit UV-vis absorption in the NIR and phosphorescence spectra (in EtOH glass at 77 K), depending on the derivative, between ~950 to 1200 nm. Their phosphores-cence yields are lower and phosphorescence lifetimes shorter when compard to those for their precursor complex, [2,3-dioxoporphyrinato]platinum(II).

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pp. 394–400Synthesis of azulitriphyrin(2.1.1)Tetsuo Okujima*, Hayato Inaba, Shigeki Mori, Masayoshi Takase and Hidemitsu Uno

A ring-contracted carbaporphyrin, azulitriphyrin(2.1.1), was synthesized via intramolecular McMurry coupling reaction. Absorption, NMR spectra and NICS calculations of protonated azulitriphyrin(2.1.1) revealed its Hückel aromatic character as a 14π porphyrinoid.

pp. 401–409A new type of multibenzyloxy-wrapped porphyrin sensitizers for developing efficient dye-sensitized solar cellsYingying Chen, Kaiwen Zeng, Chengjie Li, Xiujun Liu and Yongshu Xie*

A new class of multibenzyloxy-wrapped porphyrin sensitizers XW52 and XW53 have been designed and synthesized. As a result, a high efficiency of 9.6% was successfully achieved for the cosensitization system of XW53 + PT-C6. These results provide an effective approach for designing efficient por-phyrin dyes by introducing multiple benzyloxy groups to the porphyrin meso-phenyl groups.

pp. 410–415Phthalocyanine-corannulene conjugates: Synthesis, complexation studies with a pyridyl-functionalized C60 fullerene, and photophysical propertiesJuan A. Suanzes, Sumit Chaurasia, Rafael M. Krick Calderon, Dirk M. Guldi*, Giovanni Bottari* and Tomás Torres*

The synthesis of some novel Zn(II)Pc-corannulene conjugates is presented, and their complexation ability towards a pyridyl-functionalized C60 fullerene through metal-ligand supramolecular interactions was investigated by means of photo-physical and electrochemical techniques.

pp. 416–423Bis-palladium(II) complex of doubly N-confused octaphyrin(1.1.1.1.1.1.1.1): Möbius aromaticity and chiroptical propertiesBiju Basumatary, Koki Mitsuno, Masatoshi Ishida* and Hiroyuki Furuta*

A novel bis-palladium(II) complex of doubly N-confused octaphyrin adopting a Möbius-twisted topological structure was synthesized. Due to the effective 36π-electronic delocalization over the Möbius twisted octaphyrin scaffold, the bis-palladium(II) complex of doubly N-confused octaphyrin adopted a Möbius-twisted topological structure. The topologically chiral enantiomers were successfully separated as (P)- and (M)-twisted forms exhibiting an absorption anisotropy factor of gabs = 0.009 in the NIR region (λ = 823 nm).

pp. 440–447Synthesis and biological studies of amphiphilic carbazole pyridinium conjugatesVijayalakshmi Pandey, Hilal Rather, Sarla Yadav, Rajesh Vasita and Iti Gupta*

Water soluble carbazole-pyridinium conjugates having long alkyl chains were successfully synthesized and characterized. The presence of a pyridinium ring on the carbazole skeleton resulted in the considerable red shifts in their absorp-tion (50 nm) and emission (143–147 nm) spectra, along with large Stokes shifts (5747–7558 cm-1). Bio-imaging studies revealed cytoplasmic distribution of these conjugates in lung cancer cells.

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pp. 424–431Dipyrrolylnaphthyridine-based Schiff-base cryptands and their selective gas adsorption properties Fei Wang, Eric Sikma, Zhiming Duan, Chuanhu Lei, Zhan Zhang*, Simon M. Humphrey* and Jonathan L. Sessler*

New cryptands were synthesized through Schiff base condensation reaction between dialdehydes and triamines. Gas adsorption studies in the solid state revealed a preference for CO2 over other test gases (N2, H2, O2 and CH4).

pp. 432–439Synthesis of A2B-type 22-oxacorroles bearing two different five-membered heterocycles at meso positionsUmasekhar Booruga and Mangalampalli Ravikanth*

A series of A2B-type 22-oxacoroles containing either one six-membered aryl group along with two five-membered heterocycles such as pyrrole, furan and thiophene or all three different five-membered heterocycles at meso positions were synthesized, and the effect of five-membered heterocycles on electronic properties of 22-oxacorroles was studied.

pp. 448–455Extending a porphyrin chromophore via fusion with naphthalene Jan P. Lewtak, Beata Koszarna, Marek K. Charyton and Daniel T. Gryko*

The presence of two electron-rich dimethoxynaphthalene moieties at the meso position of the porphyrin core enabled double intramolecular oxidative aromatic coupling to occur. The use of iron(III)perchlorate hydrate and iron(III) triflate is advantageous in oxidative coupling of porphyrins not leading to concomitant chlorination.

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pp. 456–464Synthesis of highly water soluble tetrabenzoporphyrins and their application toward photodynamic therapyAusten Moss, Zehua Zhou, Lin Jiang*, M. Graça H. Vicente* and Hong Wang*

Water-soluble tetrabenzoporphyrins were synthesized, characterized and evaluated as sensitizers for photodynamic therapy. These tetrabenzoporphyrins displayed high phototoxicity with good IC50 values.

pp. 465–472Construction of secondary coordination sphere boosts electrochemical CO2 reduction of iron porphyrinsGuiyu Liu, Ying-Jie Fan and Jun-Long Zhang*

Inspired by the biological CO2 reduction procedure, iron porphyrins with ortho-amino-substitution (Fe-1) and para-amino-substitution (Fe-2) were synthesized. Compared with (Fe-2) and Fe tetra(meso-phenyl)porphyrin (Fe-3), Fe-1 exhibits improved catalytic turnover frequency (TOF), lower overpotential, and higher selectivity in electrochemical CO2 reduction reactions. DFT calculation also supports that hydrogen bonds formed between amino group and CO2 stablizes the [Fe-CO2]

2- adduct.

pp. 473–479Selective anion transport mediated by strap-extended calixpyrrolesHarriet J. Clarke, Xin Wu, Mark E. Light and Philip A. Gale*

The anion binding and transport properties of two novel bis-triazole-function-alized calixpyrroles with extended straps are compared to previously reported shorter-strap analogues known to exhibit high Cl- > H+ transport selectivity. We demonstrate improved chloride transport activities of the strap-extended com-pounds that likely benefits from increased lipophilicity. The results are instruc-tive for future design of ideal anion transporters with potent activity and high selectivity against proton leakage.

pp. 480–488Ni(II)porphyrins as pH dependent light-driven coordination-induced spin-state switches (LD-CISSS) in aqueous solutionJannis Ludwig, Jens Gröbner, Marcel Dommaschk, Lukas M. Huber, Morten K. Peters, Jan-Bernd Hövener and Rainer Herges*

A photoswitchable water-soluble Ni(II) porphyrin spin switch was successfully synthesized and characterized. The pH dependence of the switching behavior was investigated and the relaxivity (r1) was determined in 1H NMR spectroscopy and MRI measurements.

J. Porphyrins Phthalocyanines 2020; 24: 1–497

CONTENTS

pp. 489–497Cyclic butadiyne-linked porphyrin(2.1.2.1) oligomers Daiki Kuzuhara*, Wataru Furukawa, Naoki Aratani and Hiroko Yamada*

We report synthesis of cyclic butadiyne-linked porphyrin(2.1.2.1) oligomers. Porphyrin(2.1.2.1) shows a V-shaped structure which gives advantages to con-struction of the cyclic structures without template molecules. Cyclic butadiyne-linked porphyrin(2.1.2.1) trimers and tetramers are synthesized under Glaser–Hey coupling conditions from diethynylporphyrin(2.1.2.1) annulated with phthalimide groups that provide good solubility and stability.