scholarly journals Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

2014 ◽  
Vol 2014 ◽  
pp. 1-11 ◽  
Author(s):  
Gülşah Gümrükçü ◽  
Gülnur Keser Karaoğlan ◽  
Ali Erdoğmuş ◽  
Ahmet Gül ◽  
Ulvi Avcıata
Keyword(s):  
Singlet Oxygen ◽  
Quantum Yields ◽  
Schiff’S Base ◽  
Fluorescence Quantum Yields ◽  
Zinc Phthalocyanines ◽  
Peripheral Position ◽  
Photochemical Properties ◽  
Group Effects

The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II) phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO), dimethylformamide (DMF), and tetrahydrofurane (THF). Among the different substituents, phthalocyanines with cinnamaldimine moieties (1cand2c) have the highest singlet oxygen quantum yields (ΦΔ) and those with nitro groups (1aand2a) have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II) phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ) in these solvents.

Influence of protonation of peripheral substituents on photophysical and photochemical properties of tetrapyrazinoporphyrazines

2010 ◽  
Vol 14 (07) ◽  
pp. 582-591 ◽  
Author(s):  
Veronika Novakova ◽  
Eva H. Mørkved ◽  
Miroslav Miletin ◽  
Petr Zimcik
Keyword(s):  
Charge Transfer ◽  
Sulfuric Acid ◽  
Singlet Oxygen ◽  
Electron Pair ◽  
Intramolecular Charge Transfer ◽  
Quantum Yields ◽  
Considerable Decrease ◽  
Fluorescence Quantum Yields ◽  
Photochemical Properties ◽  
Free Electron Pair

Octasubstituted zinc tetrapyrazinoporphyrazines with four N,N-dimethylaminophenyls and four phenyl or pyridin-3-yl substituents were synthesized and fully characterized. Their fluorescence quantum yields in DMF or pyridine were very low, almost undetectable, as a consequence of ultrafast intramolecular charge transfer. Titration of their DMF solutions with sulfuric acid led to increase of the fluorescence quantum yields by two orders of magnitude when the full protonation of peripheral substituents was achieved. Intramolecular charge transfer is no longer a favorable way of excited-state relaxation at full protonation of N,N-dimethylaminophenyl substituents because of loss of donor centers (free electron pair on its nitrogen). Similarly, singlet oxygen quantum yields also increased by two orders of magnitude when sulfuric acid was added to tetrapyrazinoporphyrazine solutions in DMF. Protonation at azomethine nitrogens of tetrapyrazinoporphyrazine macrocycle was observed at higher acid concentrations and it led to considerable decrease of fluorescence quantum yields. Octaphenyl zinc tetrapyrazinoporphyrazine and octa(pyridin-3-yl) zinc tetrapyrazinoporphyrazine were used as controls without intramolecular charge transfer. Their fluorescence and singlet oxygen quantum yields were high in DMF and decreased at higher concentrations of sulfuric acid due to protonation of azomethine nitrogens. The results suggest that the photophysical and photochemical properties of studied compounds may be controlled by changes of pH of medium.

Bis-indole substituted phthalocyanines: Photophysical and photochemical properties

2020 ◽  
Vol 25 (01) ◽  
pp. 66-74
Author(s):  
Kevser Harmandar ◽  
Esra N. Kaya ◽  
Mehmet F. Saglam ◽  
Ibrahim F. Sengul ◽  
Devrim Atilla
Keyword(s):  
Photodynamic Therapy ◽  
Singlet Oxygen ◽  
Spectral Data ◽  
Quantum Yields ◽  
Oxygen Generation ◽  
Fluorescence Quantum Yields ◽  
H Nmr ◽  
Singlet Oxygen Generation ◽  
Photochemical Properties ◽  
C Nmr

Tetra substituted peripheral and non-peripheral Zn(II) phthalocyanines were successfully synthesized employing 4-(bis(3-methyl-1H-indol-2-yl)methyl)phenol as a starting material. The structure of these synthesized compounds was confirmed using 1H NMR, [Formula: see text]C NMR, infrared (IR), UV-vis, and MALDI-TOF spectral data. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation) properties of all synthesized peripheral and non-peripheral compounds were investigated in order to determine the potential of these compounds for application in photodynamic therapy.

Photophysical and photochemical properties of newly synthesized zinc(II) and chloroindium(III) phthalocyanines substituted with 3,5-bis (trifluoromethyl)phenoxy groups

2019 ◽  
Vol 23 (07n08) ◽  
pp. 960-968 ◽  
Author(s):  
Erem Ahmetali ◽  
Göknur Yaşa Atmaca ◽  
Hande Pekbelgin Karaoğlu ◽  
Ali Erdoğmuş ◽  
Makbule Burkut Koçak
Keyword(s):  
Photodynamic Therapy ◽  
Photophysical Properties ◽  
Quantum Yields ◽  
Fluorescence Quantum Yields ◽  
Zinc Phthalocyanines ◽  
Photochemical Properties ◽  
Photocatalytic Applications

4,5-bis(3,5-bis(trifluoromethyl)phenoxy)phthalonitrile (1) and its complexes, namely 2,3,9,10,16,17,23,24-octakis[3,5-bis(trifluoromethyl)phenoxy] phthalocyaninato zinc(II) (2) and 2,3,9,-10,16,17,23,24-octakis[3,5-bis(trifluoromethyl)phenoxy]phthalocyaninato indium(III) (3) are synthesized and characterized. Aggregation of the phthalocyanines was studied in tetrahydrofuran in different concentrations. Photochemical and photophysical properties of 2 and 3 in THF were investigated. A comparison between the photophysicochemical parameters of 2 and 3 yielded that 3 is a better photosensitizer than 2. The fluorescence quantum yields (ΦF) and 1O2 formation ([Formula: see text] for compound 3 are 0.016 and 0.84, respectively. The values for compound 2 are 0.135 and 0.54, respectively. The values of indium and zinc phthalocyanines (2 and 3) could be classified as photosensitizers in the photocatalytic applications such as photodynamic therapy (PDT) of cancer.

Novel carboxylic acid terminated silicon(IV) and zinc(II) phthalocyanine photosensitizers: Synthesis, photophysical and photochemical studies

2018 ◽  
Vol 22 (11) ◽  
pp. 1010-1021 ◽  
Author(s):  
Arif Hışır ◽  
Gülşah Gümrükcü Köse ◽  
Göknur Yaşa Atmaca ◽  
Ali Erdoğmuş ◽  
Gülnur Keser Karaoğlan
Keyword(s):  
Carboxylic Acid ◽  
Singlet Oxygen ◽  
Quantum Yields ◽  
Cooh Group ◽  
Experimental Conditions ◽  
Oxygen Generation ◽  
Fluorescence Quantum Yields ◽  
H Nmr ◽  
Silicon Phthalocyanines ◽  
Photochemical Properties

In order to improve the efficacy of photochemical properties for photodynamic therapy (PDT) applications, carboxylic acid groups axially conjugated with silicon(IV) and at the peripheral position with zinc(II) phthalocyanine skeletons for new photosensitizers to investigate the influence of the COOH group positions on the photophysicochemical performance are described in this study. Silicon (IV) (3 and 5) and zinc (II) (7) phthalocyanines were characterized by UV-vis, FTIR, 1H-NMR, MALDI-TOF MS and elemental analysis spectral data. Furthermore, the photophysical (fluorescence quantum yields and fluorescence quenching studies), photochemical (photodegradation and singlet oxygen generation) and aggregation properties of the newly synthesized phthalocyanines were investigated in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solutions. The results were compared with that of zinc and silicon phthalocyanines. Singlet oxygen quantum yields ranged from 0.23 to 0.63 via Type II mechanism under the experimental conditions studied. The fluorescence of the phthalocyanine complexes (3, 5 and 7) is effectively quenched by 1,4-benzoquinone (BQ) in DMSO, DMF and THF.

Asymmetric zinc phthalocyanines substituted with a single carboxyl and triethyleneoxysulfonyl groups: synthesis, characterization and validation for photodynamic therapy

2014 ◽  
Vol 18 (10n11) ◽  
pp. 899-908 ◽  
Author(s):  
Duygu Aydın Tekdaş ◽  
Ayşe G. Gürek ◽  
Vefa Ahsen
Keyword(s):  
Photodynamic Therapy ◽  
Singlet Oxygen ◽  
Monocarboxylic Acid ◽  
Quantum Yields ◽  
Zinc Phthalocyanines ◽  
Photochemical Properties

This work describes modular pathway towards the synthesis of new specific unsymmetrically (AB3) zinc phthalocyanines that contains three polyoxy ethylene and monocarboxylic acid groups as photosensitizers. Their photophysical and photochemical properties are studied. General trends are described for quantum yields of fluorescence, photodegradation and singlet oxygen quantum yields of these compounds. Therefore, these novel phthalocyanines could potentially be good photosensitizers for photodynamic therapy.

Influence of cyclodextrins on the fluorescence, photostability and singlet oxygen quantum yields of zinc phthalocyanine and naphthalocyanine complexes

2003 ◽  
Vol 07 (06) ◽  
pp. 439-446 ◽  
Author(s):  
Prudence Tau ◽  
Abimbola O. Ogunsipe ◽  
Suzanne Maree ◽  
M. David Maree ◽  
Tebello Nyokong
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
Inclusion Complexes ◽  
Photophysical Properties ◽  
Zinc Phthalocyanine ◽  
Quantum Yields ◽  
Fluorescence Quantum Yields ◽  
Cyclodextrin Inclusion Complexes ◽  
Cyclodextrin Inclusion ◽  
Zinc Phthalocyanines

The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine ( ZnPc ) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine ( ZnNPc ) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.

Photophysical and photochemical properties of novel phthalocyanines bearing non-peripherally substituted mercaptoquinoline moiety

2012 ◽  
Vol 16 (07n08) ◽  
pp. 845-854 ◽  
Author(s):  
Göknur Yaşa ◽  
Ali Erdoğmuş ◽  
Ahmet Lütfi Uğur ◽  
M. Kasım Şener ◽  
Ulvi Avcıata ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Electronic Spectroscopy ◽  
Quantum Yields ◽  
Solubility In Water ◽  
Fluorescence Quantum Yields ◽  
H Nmr ◽  
Good Solubility ◽  
Ft Ir ◽  
Photochemical Properties ◽  
First Time

The synthesis, photophysical and photochemical properties of nonperipherally (α) mercaptoquinoline substituted Zn(II) , TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3 , DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.

Photodynamically active phthalocyanine building blocks for click chemistry

2011 ◽  
Vol 15 (09n10) ◽  
pp. 1062-1069 ◽  
Author(s):  
Veronika Novakova ◽  
Kamil Kopecky ◽  
Miroslav Miletin ◽  
Jana Ivincova ◽  
Petr Zimcik
Keyword(s):  
Photodynamic Therapy ◽  
Singlet Oxygen ◽  
Click Chemistry ◽  
Building Blocks ◽  
Quantum Yields ◽  
Dipolar Cycloaddition ◽  
Chromatographic Technique ◽  
Simple Modification ◽  
Fluorescence Quantum Yields ◽  
Zinc Phthalocyanines

Synthesis of symmetrical and unsymmetrical zinc phthalocyanines from two different precursors 4,5-bis(tert-butylsulfanyl)phthalonitrile (A) and N-(3-azidopropyl)-2,3-dicyanoquinoxaline-6-carboxamide (B) is described. Congeners of AAAA, AAAB, ABAB and AABB type were isolated by a chromatographic technique, however, the congener of BBBB type had to be prepared in a separate reaction. The adjacent and opposite isomers were also separated and fully characterized. Isolated phthalocyanines contained different number of azide groups, a substrate for highly efficient Cu(I) -catalyzed azide-alkyne 1,3-dipolar cycloaddition ("click chemistry"). All phthalocyanines absorbed strongly (ε over 150 000 M-1.cm-1) over 700 nm. Their singlet oxygen quantum yields were determined in DMF and ranged from 0.63 to 0.79, fluorescence quantum yields in DMF were considerably lower in the range 0.03–0.06. All these properties make them suitable building blocks for a simple modification and a synthesis of phthalocyanines with better tuned properties for photodynamic therapy.

Peripherally carboxylic acid substituted asymmetric zinc(II) phthalocyanines: Synthesis and photophysicochemical properties

2019 ◽  
Vol 23 (11n12) ◽  
pp. 1355-1364 ◽  
Author(s):  
Gülenay Tunç ◽  
Mohamad Albakour ◽  
Vefa Ahsen ◽  
Ayşe Gül Gürek
Keyword(s):  
Carboxylic Acid ◽  
Singlet Oxygen ◽  
Acid Group ◽  
Quantum Yields ◽  
Cooh Group ◽  
Ionization Mass ◽  
Oxygen Generation ◽  
Fluorescence Quantum Yields ◽  
Photochemical Properties ◽  
Photovoltaic Technologies

Four asymmetric Zn(II) phthalocyanines (Pc1–Pc4) bearing a carboxylic acid group in the peripheral position have been designed and synthesized to investigate the influence of the distance between COOH group and the phthalocyanine core on their photophysical and photochemical properties. The novel phthalocyanine complexes were characterized by [Formula: see text]H, [Formula: see text]C NMR, IR, and UV-vis spectroscopies, elemental analysis and matrix-assisted laser desorption ionization mass spectrometry (MALDI). The aggregation behavior, photophysical and photochemical properties such as fluorescence lifetime and quantum yields and singlet oxygen quantum yields of Pc1–Pc4 were explored in tetrahydrofuran (THF) to the determination of the potential use of these novel phthalocyanines as photosensitizers for different applications such as photovoltaic technologies and photodynamic therapy (PDT). Pc1–Pc4exhibited high singlet oxygen generation quantum yields (0.84, 0.66, 0.88 and 0.65, respectively). Fluorescence quantum yields could be obtained for Pc1, Pc2, Pc3 and Pc4 (0.13, 0.31, 0.10 and 0.25, respectively) in THF.

New soluble 4-(4-formyl-2,6-dimethoxyphenoxy) substituted phthalocyanines: Synthesis, characterization, photophysical and photochemical properties

2021 ◽  
pp. 1-10
Author(s):  
Ibrahim Erden ◽  
Betül Karadoğan ◽  
Fatma Aytan Kılıçarslan ◽  
Göknur Yaşa Atmaca ◽  
Ali Erdoğmuş
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
Fluorescence Quantum Yield ◽  
Metal Ion ◽  
Mass Spectra ◽  
Quantum Yields ◽  
Therapeutic Outcomes ◽  
Ft Ir ◽  
Photochemical Properties ◽  
New Compounds

This work describes the synthesis, spectral and fluorescence properties of bis 4-(4-formyl-2,6-dimethoxyphenoxy) substituted zinc (ZnPc) and magnesium (MgPc) phthalocyanines. The new compounds have been characterized by elemental analysis, UV-Vis, FT-IR, 1H-NMR and mass spectra. Afterward, the effects of including metal ion on the photophysicochemical properties of the complexes were studied in biocompatible solvent DMSO to analyze their potential to use as a photosensitizer in photodynamic therapy (PDT). The fluorescence and singlet oxygen quantum yields were calculated as 0.04–0.15 and 0.70–0.52 for ZnPc and MgPc, respectively. According to the results, MgPc has higher fluorescence quantum yield than ZnPc, while ZnPc has higher singlet oxygen quantum yield than MgPc. The results show that the synthesized complexes can have therapeutic outcomes for cancer treatment.

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