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Special Issue "Phthalocyanines and Porphyrins"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: 15 February 2021.

Special Issue Editors

Prof. M. Salomé Rodríguez-Morgade
Website
Guest Editor
Universidad Autónoma de Madrid, Madrid, Spain
Interests: organic Synthesis; phthalocyanines; subporphyrazines; porphyrazines; subphthalocyanines; expanded analogues; molecular photovoltaics; PDT; artificial photosynthesis
Prof. Soji Shimizu
Website
Guest Editor
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 890-0395, Japan
Interests: porphyrin and phthalocyanine Chemistry; BODIPY; supramolecular Chemistry; near-infrared chromophores; photophysics

Special Issue Information

Dear Colleagues,

We are happy to be Guest Editors of this Special Issue of Molecules, dedicated to “Porphyrins and Phthalocyanines”. Porphyrins constitute a family of macrocycles that are ubiquitous in nature, playing important roles in numerous biological functions. Their 18 p-electron, aromatic, tetrapyrrolic structure represents far more than the sum of its parts, giving rise to a variety of physicochemical properties that cannot be deduced from those of pyrroles. Although the beginnings of porphyrin chemistry can be traced back to Hans Fischer in the 1930s, the synthesis of these macrocycles, as well as the preparation of new congeners, has been a matter of continuing scientific interest. Phthalocyanines represent the best known synthetic porphyrin analogues, being one of the most widely studied macrocyclic compounds. In addition, the synthesis of expanded, contracted, and intrinsically unsymmetrical porphyrin and phthalocyanine analogues remains an expanding topic. The scope of porphyrin science is enormous, ranging from chemical synthesis and molecular characterization to supramolecular organization, spectroscopy, electrochemistry, bioinorganic chemistry, photochemistry and photophysics, clinical medicine, and materials science, among others. This Special Issue is aimed at covering recent advances in the synthesis, characterization, and applications of porphyrins, phthalocyanines, and their analogues. We hope that these fields will be represented by both reviews and original chemical research reports that represent your contributions to this volume.

Prof. M. Salomé Rodríguez-Morgade
Prof. Soji Shimizu
Guest Editors

Manuscript Submission Information

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Keywords

  • porphyrin
  • phthalocyanine
  • porphyrazine
  • contracted porphyrins and phthalocyanines
  • expanded porphyrins and phthalocyanines
  • synthesis
  • supramolecular organization
  • photophysics
  • photochemistry
  • applications

Published Papers (8 papers)

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Research

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Open AccessCommunication
Selective Intramolecular Dehydrocyclization of Co-Porphyrin on Au(111)
Molecules 2020, 25(17), 3766; https://doi.org/10.3390/molecules25173766 - 19 Aug 2020
Abstract
The on-surface C–H bond activation and coupling reaction is a powerful approach to constructing fine-tuned surface nanostructures. It is quite challenging to control its regioselectivity due to the inertness of the C–H bond involved. With scanning tunneling microscopy/spectroscopy and theoretical calculations, the C–H [...] Read more.
The on-surface C–H bond activation and coupling reaction is a powerful approach to constructing fine-tuned surface nanostructures. It is quite challenging to control its regioselectivity due to the inertness of the C–H bond involved. With scanning tunneling microscopy/spectroscopy and theoretical calculations, the C–H activation and sequential intramolecular dehydrocyclization of meso-tetra(p-methoxyphenyl)porphyrinatocobalt(II) was explored on Au(111), showing that the methoxy groups in the molecule could kinetically mediate the selectivity of the intramolecular reaction over its intermolecular coupling counterpart. The experimental results demonstrate that the introduced protecting group could help augment the selectivity of such on-surface reaction, which can be applied to the precise fabrication of functional surface nanostructures. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Open AccessArticle
NIR Absorbing AzaBODIPY Dyes for pH Sensing
Molecules 2020, 25(16), 3689; https://doi.org/10.3390/molecules25163689 - 13 Aug 2020
Cited by 1
Abstract
Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, [...] Read more.
Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Open AccessArticle
Comparative Study of Conduction Mechanisms in Disodium Phthalocyanine-Based Organic Diodes for Flexible Electronics
Molecules 2020, 25(16), 3687; https://doi.org/10.3390/molecules25163687 - 13 Aug 2020
Abstract
In the current work, flexible diodes with flat heterojunction and dispersed heterojunction architecture were manufactured with to study the behavior of thin films of disodium phthalocyanine (Na2Pc). The thin film devices, using the electronic acceptor tetracyano-π-quinodimethane (TCNQ), were fabricated by high-vacuum [...] Read more.
In the current work, flexible diodes with flat heterojunction and dispersed heterojunction architecture were manufactured with to study the behavior of thin films of disodium phthalocyanine (Na2Pc). The thin film devices, using the electronic acceptor tetracyano-π-quinodimethane (TCNQ), were fabricated by high-vacuum thermal evaporation with annealing post-treatment in order to optimize their behavior. Theoretical calculations based on density functional theory (DFT) with dispersion force analysis were carried out in order to simulate molecular interactions and to establish the nature of the weak interactions between the Na2Pc and TCNQ fragments. In the optimized structure of the coupled Na2Pc-TCNQ, the electronic relationship between phthalocyanine and TCNQ was observed to be through hydrogen bonds with bond lengths of 2.94 and 3.13 Å. Dispersed heterojunction device current density values were considerably larger than those of the flat heterojunction device. Barrier heights of 1.024 and 0.909 eV and charge mobilities of 10−10 and 10−9 m2/Vs for the flat heterojunction device and the dispersed heterojunction device, respectively, were observed. A small effect was observed on the electrical properties by thermal annealing on the flat heterojunction device. The threshold voltage decreased from 1.203 to 1.147 V and φb decreased by 0.001 eV. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Open AccessFeature PaperArticle
A Leopard Cannot Change Its Spots: Unexpected Products from the Vilsmeier Reaction on 5,10,15-Tritolylcorrole
Molecules 2020, 25(16), 3583; https://doi.org/10.3390/molecules25163583 - 06 Aug 2020
Abstract
The reaction of 5,10,15-tritolylcorrole with 3-dimethylaminoacrolein (3-DMA) and POCl3 gives a further example of the rebel reactivity of this contracted macrocycle. While no evidence was obtained for the formation of the expected β-acrolein corrole, the inner core substituted N21,N22-3-formylpropylcorrole and the 10-acrolein [...] Read more.
The reaction of 5,10,15-tritolylcorrole with 3-dimethylaminoacrolein (3-DMA) and POCl3 gives a further example of the rebel reactivity of this contracted macrocycle. While no evidence was obtained for the formation of the expected β-acrolein corrole, the inner core substituted N21,N22-3-formylpropylcorrole and the 10-acrolein isocorrole were the reaction products. By increasing the temperature or the amount of the Vilsmeier reagent, the 10-isocorrole became the unique reaction product. The formation of the isocorrole by electrophilic attack of the Vilsmeier reagent to the 10-position of the corrole is unprecedented in the porphyrinoids field and it could pave the way for a novel route to the preparation of stable isocorroles. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Open AccessCommunication
Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes
Molecules 2020, 25(12), 2753; https://doi.org/10.3390/molecules25122753 - 15 Jun 2020
Abstract
Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex 4 was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex 3 and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex 6 was obtained upon treatment [...] Read more.
Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex 4 was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex 3 and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex 6 was obtained upon treatment of bis-Pd(II) [26]hexaphyrin 5 with [RuCl2(p-cymene)]2 under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for 4 and 6 by 1H-NMR spectral and theoretical calculations. These results are accounted for in terms of possible resonance contributors of hexaphyrin di- and tetraanion ligands. Thus, π-metal coordination has been shown to be effective for modulation of the overall aromaticity. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Open AccessArticle
A Hybrid Nanomaterial Based on Single Walled Carbon Nanotubes Cross-Linked via Axially Substituted Silicon (IV) Phthalocyanine for Chemiresistive Sensors
Molecules 2020, 25(9), 2073; https://doi.org/10.3390/molecules25092073 - 29 Apr 2020
Cited by 1
Abstract
In this work, the novel hybrid nanomaterial SWCNT/SiPc made of single walled carbon nanotubes (SWCNT) cross-linked via axially substituted silicon (IV) phthalocyanine (SiPc) was studied as the active layer of chemiresistive layers for the detection of ammonia and hydrogen. SWCNT/SiPc is the first [...] Read more.
In this work, the novel hybrid nanomaterial SWCNT/SiPc made of single walled carbon nanotubes (SWCNT) cross-linked via axially substituted silicon (IV) phthalocyanine (SiPc) was studied as the active layer of chemiresistive layers for the detection of ammonia and hydrogen. SWCNT/SiPc is the first example of a carbon-based nanomaterial in which an axially substituted phthalocyanine derivative is used as a linker. The prepared hybrid material was characterized by spectroscopic methods, thermogravimetry, scanning and transmission electron microscopies. The layers of the prepared hybrid were tested as sensors toward ammonia and hydrogen by a chemiresistive method at different temperatures and relative humidity as well as in the presence of interfering gases like carbon dioxide, hydrogen sulfide and volatile organic vapors. The hybrid layers exhibited the completely reversible sensor response to both gases at room temperature; the recovery time was 100–200 s for NH3 and 50–120 s in the case of H2 depending on the gas concentrations. At the relative humidity (RH) of 20%, the sensor response was almost the same as that measured at RH 5%, whereas the further increase of RH led to its 2–3 fold decrease. It was demonstrated that the SWCNT/SiPc layers can be successfully used for the detection of both NH3 and H2 in the presence of CO2. On the contrary, H2S was found to be an interfering gas for the NH3 detection. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Open AccessArticle
In Vitro Anti-Leishmanial Effect of Metallic Meso-Substituted Porphyrin Derivatives against Leishmania braziliensis and Leishmania panamensis Promastigotes Properties
Molecules 2020, 25(8), 1887; https://doi.org/10.3390/molecules25081887 - 19 Apr 2020
Cited by 1
Abstract
In this study, a family of porphyrins based on 5,10,15,20-Tetrakis(4-ethylphenyl)porphyrin (1, Ph) and six metallo-derivatives (Zn2+(2, Ph-Zn), Sn4+(3, Ph-Sn), Mn2+ (4, Ph-Mn), Ni2+ (5, Ph-Ni), Al3+ [...] Read more.
In this study, a family of porphyrins based on 5,10,15,20-Tetrakis(4-ethylphenyl)porphyrin (1, Ph) and six metallo-derivatives (Zn2+(2, Ph-Zn), Sn4+(3, Ph-Sn), Mn2+ (4, Ph-Mn), Ni2+ (5, Ph-Ni), Al3+ (6, Ph-Al), and V3+ (7, Ph-V)) were tested as photosensitizers for photodynamic therapy against Leishmania braziliensis and panamensis. The singlet oxygen quantum yield value (ΦΔ) for (17) was measured using 1,3-diphenylisobenzofuran (DPBF) as a singlet oxygen trapping agent and 5,10,15,20-(tetraphenyl)-porphyrin (H2TPP) as a reference standard; besides, parasite viability was estimated by the MTT assay. After metal insertion into the porphyrin core, the ΦΔ increased from 0.76–0.90 and cell viability changed considerably. The ΦΔ and metal type changed the cytotoxic activity. Finally, (2) showed both the highest ΦΔ (0.90) and the best photodynamic activity against the parasites studied (IC50 of 1.2 μM). Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Review

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Open AccessReview
BODIPY- and Porphyrin-Based Sensors for Recognition of Amino Acids and Their Derivatives
Molecules 2020, 25(19), 4523; https://doi.org/10.3390/molecules25194523 - 02 Oct 2020
Abstract
Molecular recognition is a specific non-covalent and frequently reversible interaction between two or more systems based on synthetically predefined character of the receptor. This phenomenon has been extensively studied over past few decades, being of particular interest to researchers due to its widespread [...] Read more.
Molecular recognition is a specific non-covalent and frequently reversible interaction between two or more systems based on synthetically predefined character of the receptor. This phenomenon has been extensively studied over past few decades, being of particular interest to researchers due to its widespread occurrence in biological systems. In fact, a straightforward inspiration by biological systems present in living matter and based on, e.g., hydrogen bonding is easily noticeable in construction of molecular probes. A separate aspect also incorporated into the molecular recognition relies on the direct interaction between host and guest with a covalent bonding. To date, various artificial systems exhibiting molecular recognition and based on both types of interactions have been reported. Owing to their rich optoelectronic properties, chromophores constitute a broad and powerful class of receptors for a diverse range of substrates. This review focuses on BODIPY and porphyrin chromophores as probes for molecular recognition and chiral discrimination of amino acids and their derivatives. Full article
(This article belongs to the Special Issue Phthalocyanines and Porphyrins)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Porphyrins as NIR photoinitiators of polymerization
Authors: Fréderic Dumur
Affiliation: Aix Marseille Univ, CNRS, ICR, UMR 7273, F-13397 Marseille, France

Title: Encountering of porphyrins with silica matrices. Performance versus functionality
Authors: Gheorghe Fagadar-Cosma
Affiliation: Faculty of Industrial Chemistry and Environmental Engineering, Politehnica University Timisoara, PtaVictoriei 2, 300006 Timisoara, Romania

Title: Green-solvents approaches for the synthesis of metallophthalocyanines
Authors: Gloria Zanotti; Giovanna Pennesi; Anna Maria Paoletti
Affiliation: Istituto di Struttura della Materia, Consiglio Nazionale delle Ricerche
Abstract: This work aims at studying the potential replacement of the toxic solvents that are normally employed for the synthesis of phthalocyanines, e.g. dimethylaminoethanol, nitrobenzene and -chloronaphthalene, with greener alternatives. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles with the aim of developing new sustainable and scalable synthetic protocols with comparable or lower E-factors and costs with respect to the existing ones. Salts of several divalent first-transition metal cations [(Co(II), Ni(II), Cu(II) and Zn(II)) were used and different bases were tested, depending on the chosen substrates and reaction conditions. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metals in terms of reactivity in the new reaction media, resulting in a general Cu > Ni > Co > Zn trend, while tetra-tert-butyl substituted derivatives were investigated to evaluate the influence of an alkyl bulky moiety on the tetramerization efficiency. Furthermore, the statistical synthesis of the unsymmetrical tri-tert-butyl-iodo zinc phthalocyanine in glycerol/anisole with KOH as a base gave a 26% yield, comparable with those already published in literature. Our results provide insights into the investigation of new reaction environments and in the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of macrocyclic molecules and intermediates with high added value.

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