II ) And Indium Research Articles

A3B type asymmetric metallo phthalocyanines bearing carboxylic acid and tert-butyl groups: Photophysical, photochemical and aggregation properties

In this study, A3B type asymmetric magnesium(II), zinc(II) and indium(III)chloro phthalocyanine derivatives bearing carboxylic acid and tert-butyl groups were synthesized and their photochemical, photophysical and aggregation properties for photodynamic therapy (PDT) application were investigated. In the first part of the study; phthalonitriles, which are the starting materials, were synthesized and then different phthalocyanine compounds were obtained from the synthesized phthalonitriles in the second part. The synthesized compounds were characterized using different techniques. At the same time, the photophysical and photochemical properties of the synthesized compounds were also investigated. The calculated singlet oxygen quantum values in DMSO are 0.30 for MgPc, 0.72 for ZnPc, and 0.62 for InPc in and these values in DMF are 0.25 for MgPc, 0.68 for ZnPc, and 0.60 for InPc after photochemical studies. The obtained results proved that the contribution of the substituents increased the therapeutic efficacy. Finally, our results show that all Pc derivatives have displayed desirable singlet oxygen, photodegradation, fluorescence and aggregation properties for PDT studies.

Phthalocyanine photosensitizers with bathochromic shift, of suitable brightness, capable of producing singlet oxygen with effective efficiency

• New phthalocyanine derivatives as photosensitizers were designed and synthesized. • The phthalocyanines dissolve well in common solvents without aggregation. • The phthalocyanines have improved fluorescence and optical absorption properties. • The phthalocyanines have improved photochemical properties and photostability. • The phthalocyanines can be used as photosensitizers in photocatalytic applications. In this study, novel 3-(2,3-dimethoxyphenoxy)phthalonitrile 2 and its non-peripheral tetra-2,3-dimethoxyphenoxy substituted metal-free phthalocyanine 3 compounds were synthesized. Then, the magnesium(II), zinc(II), and indium(III) acetate phthalocyanine complex derivatives ( 4-6 ) of compound 3 were synthesized using the corresponding metal salts by the template effect. The structures of novel phthalonitrile derivative 2 and its metal-free phthalocyanine compounds 3 as well as different metal-containing phthalocyanine complexes ( 4-6 ) were characterized by elemental analysis, FTIR, UV-vis, 1 H NMR, and MALDI-TOF mass spectroscopic techniques. The phthalocyanines ( 3-6 ) can dissolve well in different polar protic, polar aprotic, and non-polar solvent types without aggregation, with maximum absorption intensity and bathochromic effect. Photophysicochemical properties of the phthalocyanines ( 3-6 ) in dimethyl sulfoxide and important spectral parameter values such as molar extinction coefficient, oscillator strength, and electrical dipole strength were determined, and they were also compared with each other and with their unsubstituted counterparts. It was determined that the phthalocyanines ( 3-6 ) have suitable and sufficient fluorescence quantum yields, fluorescence lifetimes, fluorescence brightness, and other photophysical properties, as well as singlet oxygen generation, phototoxic power, and photostability properties. The phthalocyanines ( 3-6 ), particularly zinc(II) and indium(III) acetate phthalocyanines have remarkable potential for use as Type II photosensitizers for cancer therapy in photodynamic therapy. The phthalocyanines ( 3-6 ) may be promising candidates for various applications as photosensitizers for photodynamic therapy, especially in combination with fluorescent imaging.

Novel cationic-chalcone phthalocyanines for photodynamic therapy eradication of S. aureus and E. coli bacterial biofilms and MCF-7 breast cancer

New tetrasubstituted zinc (II) and indium (III) phthalocyanines bearing dimethylamino chalcone group (complexes 3 and 4) as well as their quaternized analogs (3a and 4a) have been assessed for their photodynamic therapy (PDT) of cancer as well as photodynamic antimicrobial chemotherapy activities against biofilms and planktonic cultures of pathogenic bacteria of Staphylococcus aureus and Escherichia coli. Compared to the non-quaternized phthalocyanines 3 and 4, the cationic phthalocyanines 3a and 4a exhibit a higher photodynamic inactivation against the planktonic cells with log reduction values above 9 at a concentration of 1.25 µM. This was attributed to the positive charge which enhances cellular uptake. More interestingly, 3a and 4a show a higher photodynamic inactivation (less than 3% of S. aureus survived) on their biofilm counterparts thanks to their stronger affinity to these cells. 3a and 4a Pcs also exhibited interesting PDT activity against MCF-7 cancer cells giving IC50 values of 17.9 and 7.4 μM, respectively following 15 min irradiation. The obtained results in this work show that the positively charged phthalocyanines 3a and 4a are potential antibacterial photosensitizers that show some selectivity toward the Gram-positive and Gram-negative bacteria as well as MCF-7 breasts cancer cells.

Phthalocyanines bearing silazane group for colorectal cancer

The synthesis of bis(trimethylsilyl)amine substituted zinc(II), and indium(III) chloride phthalocyanine complexes have been performed. The obtained compounds were characterized by spectroscopic methods. All synthesized phthalocyanine derivatives were evaluated for cytotoxic, genotoxic, and apoptotic activities on LoVo cell lines which are the standard colorectal cancer cell lines derived from metastatic site: left supraclavicular region. Non-peripheral silazane substituted zinc phthalocyanine (5) showed quite different behavior from all the other compounds analyzed and found to be the best cytotoxic, genotoxic, and apoptotic compound. All derivatives showed no proliferative effect at all doses. All phthalocyanine compounds increased cytotoxicity, DNA damage, apoptosis, and intracellular ROS dose-dependent manner. To explain and verify in vitro tests, phthalocyanine compound structures were optimized using density functional theory, and in silico molecular docking studies on B-DNA dodecamer were performed. Both the experimental and theoretical findings comply with each other.

Spectroscopic, photophysical and photochemical properties of newly metallo-phthalocyanines containing coumarin derivative

The new, well-soluble and non-aggregated peripheral or non-peripheral tetra-ethyl 7-oxy-4,8-dimethylcoumarin-3-propanoate substituted magnesium (II), zinc (II) and indium (III) acetate phthalocyanines were synthesized. They were characterized by widely known spectroscopic methods such as UV–vis, IR, MALDI-TOF Mass, 1H NMR spectroscopies and elemental analysis. Photophysical and photochemical properties were studied in N, N-dimethylformamide to determine the usability of each of these phthalocyanines as photosensitizers. The influences of the position and presence of the coumarin derivative at the phthalocyanine skeleton and metal’ nature in the phthalocyanine cavity on photophysical and photochemical properties were investigated by comparing with previous analogues (magnesium, zinc, and indium phthalocyanines containing coumarin derivative with different functional groups). The spectroscopic, photophysical, photochemical data and results obtained for each of these phthalocyanines show that they may have the potential to be used as photosensitizers in photodynamic therapy.

Potential photosensitizer candidates for PDT including 7-oxy-3-thiomethylphenyl coumarino-phthalocyanines

In this work, the novel phthalonitrile derivatives and their peripheral/nonperipheral phthalocyanine analogues including 7-oxy-3-(p-thiomethylphenyl) coumarin were synthesized and purified. All these novel compounds were characterized by common characterization methods such as FT-IR, UV–vis, MALDI-TOF, 1H-NMR and elemental analysis. Furthermore, the photochemical and photophysical properties of newly synthesized zinc(II) and indium(III) phthalocyanines were investigated in N,N-dimethylformamide (DMF) solutions. The substituent effect toward the phthalocyanine center and the metal effect on the photophysicochemical properties were also investigated.

7‐Oxy‐3,4‐cyclohexenecoumarin Carrying Novel Zinc(II) and Indium(III) Acetate Phthalocyanines: Synthesis, Characterization, Photophysical and Photochemical Properties

AbstractIn this study, 7‐hydroxy‐3,4‐cyclohexenecoumarin (1), two new phthalonitriles, 7‐(2,3‐dicyanophenoxy)‐3,4‐cyclohexene‐coumarin (2), 7‐(3,4‐dicyanophenoxy)‐3,4‐cyclohexenecoumarin (3), were prepared. The phthalonitrile derivatives 2 and 3 were converted to the respective non‐peripheral tetra, peripheral tetra 7‐oxy‐3,4‐cyclohexenecoumarin substituted zinc(II) (4,6) and indium(III)acetate phthalocyanine (5,7) derivatives. All novel purified compounds (2‐7) were characterized by elemental analysis, FT‐IR, UV‐vis, 1H NMR, 13C NMR, MALDI‐TOF mass data. The spectral, photophysical (fluorescence quantum yields and lifetimes), and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of the synthesized Pcs (4‐7) were studied in DMF, and the results were compared to determine the effects of the locations of substituents and the diversity of the central metal atom on these properties. The 7‐oxy‐3,4‐cyclohexenecoumarin bearing phthalocyaninatozinc(II) and indium(III)acetate complexes showed good solubility in organic solvents such as chloroform, dichloromethane, tetrahydrofuran, acetone, DMF and DMSO. The fluorescence quenching behavior were investigated using 1,4‐benzoquinone as a quencher. They have an acceptable level of singlet oxygen production, which determines the usability of phthalocyanines in photodynamic therapy applications and demonstrated appropriate photodegradation. The thermal properties of Pcs (4‐7) were also investigated.

Rupe Rearrangement Studies in Liquid Sulfur Dioxide

Copper (II) and indium (III) triflate catalyzes the Rupe rearrangement of propargylic alcohols in liquid sulfur dioxide as the reaction medium. 1-Ethynylcyclohexanol and 1-(phenylethynyl) cyclohexan-1-ol were used as the model substrates and the expected 1-(cyclohex-1-en-1-yl) ethanone and 1-(cyclohex-1-en-1-yl)-2-phenylethanone were obtained in average yields.

Synthesis, characterization and photovoltaic behaviours of peripheral and non-peripheral tetra-[4-(4-octylpiperazin-1-yl)phenoxy] substituted zinc(II), cobalt(II), copper(II) and indium(III) phthalocyanines

The synthesis of zinc(II), cobalt(II), copper(II) and indium(III)(OAc) phthalocyanines carrying four 4-(4-octylpiperazin-1-yl)phenoxy moieties in peripheral/non-peripheral positions were performed by the cyclotetramerization of compounds 4-[4-(4-octylpiperazin-1-yl)phenoxy]phthalonitrile or 3-[4-(4-octylpiperazin-1-yl)phenoxy]phthalonitrile with respective metal salts. The novel phthalonitriles and phthalocyanines were characterized by elemental and spectroscopic analysis, including 1H NMR, 13C NMR, FT-IR, UV–Vis spectral and MALDI-TOF mass data. To clarify the influence of the position of substituent group and the variety of the central metal atom on the photovoltaic performance, bulk heterojunction devices by using phthalocyanines with different blend ratio, as donor was fabricated and characterized.

Butanol synthesis from ethanol over CuMgAl mixed oxides modified with palladium (II) and indium (III)

Ethanol conversion to butanol was investigated over mixed oxides derived from hydrotalcites modified with copper, palladium or indium. The reaction was carried out in the 403–573 K temperature range using stainless steel reactors. The presence of indium or palladium in the catalyst influences the temperature of reaction so that it was possible obtain butanol at temperature as low as 423 K. This is in line with the fact that the addition of metals with high hydrogen-transfer capacity makes faster all steps of the reaction with great energy saving. The best selectivity to butanol (65%) was achieved using In-CuMgAl catalysts with 3% of ethanol conversion at a temperature as low as 443 K.

Synthesis and characterization of 6,8-di-tert-butyl-3-[p-(propynyl)phenoxy]coumarin substituted phthalocyanines and investigation of their photophysical and photochemical properties

The new compound, 6,8-di-tert-butyl-3-[p-(propynyl)phenoxy]coumarin 2 was prepared by the reaction of 6,8-di-tert-butyl-3-(p-hydroxyphenyl)coumarin 1 with propargyl bromide. The synthesized 6,8-di-tert-butyl-3-[p-(propynyl)phenoxy]coumarin was reacted with tetra-iodo zinc(II) (3) or tetra-iodo indium(III) acetate (4) phthalocyanines by the Sonogashira coupling reaction for the synthesis of the coumarin substituted phthalocyanines 5 and 6, respectively. These phthalocyanines are the first examples of the coumarin substituted phthalocyanines connected by ethynyl bond. All novel compounds synthesized in this study were fully characterized by general spectroscopic techniques such as FT-IR, UV–vis, 1H NMR, mass and elemental analysis as well. The photophysicochemical and spectral properties of zinc(II) and indium(III)OAc phthalocyanines (5 and 6) were investigated in dimethylsulfoxide (DMSO) solutions. The complexes (5 and 6) showed well solubility in most of organic solvents such as dichloromethane, THF, chloroform, DMF and DMSO. These phthalocyanines (5 and 6) exhibited good singlet-oxygen generation (ΦΔ=0.96 for 6 and ΦΔ=0.62 for 5) and appropriate photodegradation quantum yields (Φd=0.45x10−5 for 5 and Φd=0.43x10−5 for 6) in DMSO.

First investigation on the photophysical and photochemical properties of azo-bridged phthalocyanine photosensitizers

Novel azo-bridged indium(III) acetate phthalocyanine was synthesized by cyclotetramerization reaction of (E)-4-((2,5-dimethoxyphenyl)diazenyl)phthalonitrile. This phthalocyanine was fully characterized by FT-IR, 1H-NMR, UV–vis and MALDI-TOF mass spectroscopic techniques and elemental analyses as well. Additionally, the photophysical and photochemical properties of this phthalocyanine was investigated for the first time. The obtained results were compared with azo-bridged zinc(II) and metal-free phthalocyanine counterparts for determination of central metal effect on these properties. These results were also compared with unsubstituted zinc(II) and indium(III)acetate phthalocyanines for determination of substitution effect on the photophysical and photochemical properties.

Preparation, characterization and photophysicochemical properties of novel tetra 7-(diethyl 2-methylmalonatoxy)-3-(p-oxyphenyl)coumarin-substituted zinc(II) and indium(III)chloride phthalocyanines

In this study, 7-(diethyl 2-methylmalonatoxy)-3-[p-(3,4-dicyanophenoxy)phenyl]coumarin (3), 7-(diethyl 2-methylmalonatoxy)-3-[p-(2,3-dicyanophenoxy)phenyl]coumarin (4) and their related peripheral and non-peripheral tetra substituted zinc(II) (3a and 4a) and indium(III)chloride (3b and 4b) phthalocyanine derivatives were prepared for the first time. The novel phthalonitrile (3 and 4) and phthalocyanine (3a-b and 4a-b) compounds were characterized by elemental analyses and different spectroscopic techniques such as FT-IR, UV–vis, 1H NMR and MALDI-TOF mass. The spectral, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines were investigated in dimethylsulfoxide solutions. The fluorescence quenching behaviors of the studied zinc(II) phthalocyanines (3a and 4a) by 1,4-benzoquinone were also determined.

Synthesis and Characterization of Cadmium (II), Lead (II), and Indium (III) Ketoacidoximate Complexes and their Conversion to Metal Oxides

AbstractThe reaction of Cd(II), Pb(II), and In(III) salts with in situ generated pyruvic acid oxime (ketoacidoximate) of the type [O2C‐C(R)=NOH]‐, (R=CH3 or ‐CH2‐C6H5) results in five novel complexes [Cd{O2C‐C(CH2‐C6H5)=NOH}2(py)2]2 (py=C5H5N) 1, [Cd{O2C‐C(CH2‐C6H5)=NOH}2(im)2]2 (im=C3H4N2) 2, [Pb{O2C‐C(CH3)=NOH}2(py)]2 3, [Pb{O2C‐C(CH2‐C6H5)=NOH}2(dmso)]2 (dmso=dimethyl sulfoxide) 4 and (NH4)[In{O2C‐C(CH3)=NOH}4] 5. Single crystal X‐ray structure determination of 1–5 reveal mono‐nuclear In(III) and di‐nuclear, µ2‐oxo bridged Cd(II), Pb(II) complexes. 1–5 undergo thermal decomposition below 210ºC to the corresponding metal oxides.

Cadmium(II) and indium(III) complexes derived from 2-benzoylpyridine N(4)-cyclohexylthiosemicarbazone: Synthesis, crystal structures, spectroscopic characterization and cytotoxicity

Two metal complexes [Cd(L)2]·0.275H2O(1) and [In(L)2]NO3 (2) (HL=2-benzoylpyridineN(4)-cyclohexylthiosemicarbazone) have been synthesized and structurally characterized by elemental analysis, a number of spectroscopic methods (IR, UV-vis, NMR), mass spectrometry, and X-ray crystallography. The Schiff’s base ligand forms hexacoordinated complexes having octahedral geometry for Cd(II) and In(III) complexes, respectively. The synthesized compounds were tested for antiproliferative activity and showed the ability to kill HepG2 cells (human hepato cellular carcinoma) significantly, especially 2 with IC50=2.02±0.14μM. Of particular note is the fact that complex 1 has ca 12-fold lower toxicity in the normal hepatocyte QSG7701 cells than in the hepatocellular carcinoma HepG2 cells. In addition, complex 2 also exhibited excellent luminescent property. Upon the addition of 1 equiv of In3+ ion, 200-fold fluorescence enhancement of HL at λem=504nm has been observed. Moreover, the fluorescent color change (from transparent to light-green) could be observed by naked eyes under the light of 365nm. These findings can expand the applications of thiosemicarbazone derivatives in the fields of colorimetric and fluorescent probes.

Synthesis, characterization, photophysical, and photochemical properties of novel zinc(II) and indium(III) phthalocyanines containing 2-phenylphenoxy units

The synthesis of highly soluble and non-aggregated peripherally/non-peripherally Zn and In(OAc) phthalocyanines was achieved by 3-/ and 4-(2-phenylphenoxy)phthalonitrile as starting materials. The novel compounds were characterized by elemental analyses, FT-IR, 1H-NMR (for phthalonitriles), UV–vis and MALDI-TOF mass (for Pcs) spectroscopic techniques. Additionally, photophysical, photochemical and spectral properties of the phthalocyanines were reported. Especially, the indium(OAc) phthalocyanines showed good singlet oxygen quantum yields in DMSO and they can be appropriate candidates as Type II photosensitizers in photodynamic therapy (PDT) applications.

The novel 2,6-dimethoxyphenoxy substituted phthalocyanine dyes having high singlet oxygen quantum yields

The synthesis of novel peripheral or non-peripheral tetra-2,6-dimethoxyphenoxy substituted metal free, zinc(II) and indium(III) phthalocyanines was achieved. The novel compounds were characterized by IR, UV–Vis, 1H NMR, MALDI-TOF mass spectroscopies and elemental analysis as well. The effects of the substituent position and the influence of the variety of central metal ions in novel phthalocyanines, on their spectroscopic, photophysical (fluorescence quantum yields, fluorescence lifetimes) and photochemical (photodegradation, singlet oxygen) properties were also investigated in dimethylformamide (DMF). The phthalocyanines showed good singlet oxygen quantum yields, appropriate photodegradation and fluorescence behaviour. For this reason, they may be appropriate candidates Type II photosensitizers for photodynamic therapy of cancer.

High photosensitized singlet oxygen generating zinc(II) and indium(III) acetate phthalocyanines containing 6,8-di- tert -butyl-3-( p -oxyphenyl)coumarin groups

Abstract The novel 6,8-di-tert-butyl-3-(p-hydroxyphenyl)coumarin (1) and its phthalonitrile derivatives named 4-[6,8-di-tert-butyl-3-(p-oxyphenyl)coumarin]phthalonitrile (2), 3-[6,8-di-tert-butyl-3-(p-oxyphenyl)coumarin]phthalonitrile (3), 4,5-bis[6,8-di-tert-butyl-3-(p-oxyphenyl)coumarin]phthalonitrile (4) and 4-chloro-5-[6,8-di-tert-butyl-3-(p-oxyphenyl)coumarin]phthalonitrile (5) were synthesized. These phthalonitrile derivatives were also converted to the corresponding zinc(II) (2a–5a) and indium(III)(OAc) (2b–5b) phthalocyanines bearing four or eight 6,8-di-tert-butyl-3-(p-oxyphenyl)coumarin groups. All novel compounds synthesized in this study were fully characterized by elemental analysis and general spectroscopic techniques such as FT-IR, UV–vis, 1H NMR and mass. Additionally; spectral, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of 6,8-di-tert-butyl-3-(p-oxyphenyl)coumarin substituted zinc(II) and indium(III)(OAc) phthalocyanines were investigated in N,N-dimethylformamide (DMF) solutions. The effects of number or position of the substituents and the type of central metal atoms on these properties were also determined. All studied phthalocyanines showed excellent solubility in general organic solvents. They also produced good singlet-oxygen and showed appropriate photodegradation by light irradiation.

Synthesis, photochemical and photophysical properties of zinc(II) and indium(III) phthalocyanines bearing fluoroalkynyl functionalized substituents

In this work, the synthesis of a novel phthalonitrile derivative with fluoroalkynyl functionalized groups and its peripherally tetrasubstituted zinc(II) and indium(III) phthalocyanine complexes were reported. The novel phthalonitrile derivative was prepared by the metal-mediated Sonogashira cross-coupling reaction between 4-iodophthalonitrile and 1-ethynyl-3,5-difluorobenzene. Metallophthalocyanines bearing fluoroalkynyl functionalized groups (compounds 3 and 4) were obtained from the corresponding phthalonitrile derivative in the presence of the corresponding metal salts in refluxing dimethylaminoethanol as the solvent. These novel compounds were characterized by elemental analyses and spectral techniques, namely FT-IR spectrometry, 1H, 13C and 19F NMR spectroscopies, UV–Vis spectrophotometry, and mass spectrometry. The generation of singlet oxygen, photodegradation and fluorescence quantum yields, and fluorescence lifetime values of these complexes were determined in N,N-dimethylformamide. The effects of the substitution with fluoroalkynyl-functionalized groups on these parameters mentioned were also compared along with the previously synthesized tetrakis[(trifluoromethyl)phenylethynyl] substituted zinc(II) and indium(III) phthalocyanines.

Influence of heavy central atom on photoelectric, nonlinear optical, and photorefractive properties of metal phthalocyanines

Measurement of the photoelectric and photorefractive characteristics of 2,3,9,10,16,17,23,24-tetra(15-crown-5)phthalocyaninatoacetatoyttrium(III) [(15C5)4Pc]Y(OAc) has made it possible to reliably establish the features of decrease in the quantum yield of generation of charge carriers φ0 and photorefractive two-beam coupling gain Γ with an increase in the atomic weight of the central metal in a series of related gallium(III), yttrium(III), ruthenium(II), and indium (III) phthalocyaninates. These features can be due to an increase in the spin-orbit interaction constant with increasing atomic weight of the central metal, a change that leads to an increase in both the contribution of triplet excited associates to the formation of mobile charge carriers and the rate of the reverse reaction T1 → S0, which effectively inhibits the formation of charge carriers through the excited triplet state. The measurement of photoelectric and photorefractive characteristics at 1064 nm has shown that the quantum yield of electron-hole pairs in the composite polyvinylcarbazole/supramolecular assemblies of yttrium complex is φ0 = 0.6 and the two-beam coupling gain coefficient Γ is about 35 cm−1 at E0 = 120 V/μm. The dielectric susceptibility measured by the z-scan technique in a solution of the yttrium complex in tetrachloroethane (1 mg in 1 mL) is χ(3) = 4.2 × 10−10 esu.