Synthesis, photophysicochemical properties and TD-DFT calculations of tetrakis (2-benzoyl-4-chlorophenoxy) phthalocyanines

The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy

Photodynamic therapy activities of phthalocyanine-based macromolecular photosensitizers on MCF-7 breast cancer cells

Poly(oxanorbornene)s with zinc(II) phthalocyanine side chains have been synthesized by ring-opening metathesis polymerization. The incorporation of zinc(II) phthalocyanine into cationic polymer has given poly(oxanorbornene)s noteworthy photophysicochemical properties and the capacity to generate singlet oxygen under light irradiation. To investigate photosensitizer’s properties of the newly synthesized polymers P6 and P7: fluorescence (ΦF), singlet oxygen (ΦΔ) and triplet (ΦT) quantum yields of polymers have been measured in dimethyl sulfoxide and aqueous medium. Singlet oxygen quantum yields of P6 and P7 have been found to be 0.22 and 0.20 in dimethyl sulfoxide, respectively. Then, photodynamic therapy activities of polymers (P1-P7) against human breast adenocarcinoma cell line (MCF-7 cells) have been investigated. The copolymer P5 bearing pendant zinc(II) phthalocyanine and triethyl phosphonium functionalities has showed enhanced PDT activity with less than 10% viable cells at 60 μg/mL

Enhanced Light-Driven Antimicrobial Activity of Cationic Poly (oxanorbornene) s by Phthalocyanine Incorporation into Polymer as Pendants

Amphiphilic poly(oxanorbornene)s are promising synthetic polymers that mimic the structural properties and antimicrobial functions of naturally occurring antimicrobial peptides. Here, poly(oxanorbornene)s bearing pendant zinc(II) phthalocyanine and triphenyl(ethyl) phosphonium functionalities are synthesized by ring-opening metathesis polymerization (ROMP). Fluorescence, singlet oxygen and triplet quantum yields of polymers are measured in dimethyl sulfoxide and aqueous medium. The singlet oxygen quantum yields of copolymers with the highest triphenyl and triethyl phosphonium content are found to be 0.29 and 0.41, respectively. Then, antimicrobial activities of polymers against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) are investigated under both dark and light conditions. Synergistic effect of zinc(II) phthalocyanine and phosphonium-containing poly(oxanorbornene) is observed that the conjugate possessing the most triphenyl phosphonium side chains has the highest activity under light against both gram-positive and gram-negative bacterial strains after 80 min irradiation, reducing the survival of E. coli or S. aureus by 99.9999%. Hemolytic concentrations of the copolymers are found between 8 and 512 µg mL−1. Scanning electron microscopy (SEM) proves that the bacteria membrane deforms after contacting with the biocidal polymer

Pyrazole-3-carboxylic acid as a new anchoring group for phthalocyanine-sensitized solar cells

We have designed and synthesized an unsymmetrical zinc phthalocyanine (PCA-ZnPc-1) bearing an electron-withdrawing pyrazole-3-carboxylic acid anchoring group and three electron-donating tert-butyl groups as a sensitizer for dye-sensitized solar cells (DSSCs). PCA-ZnPc-1 sensitized solar cell showed a modest power conversion efficiency (1.74%), which may suffer from the flexible and non-conjugated oxygen linker on the sensitizer. However, the obtained efficiency is found to be three to four times higher than that of the unsymmetrical ones bearing only carboxylic acid due to the combination of pyrazole and carboxylic acid moieties within the same anchoring group, which enhances the binding of the dye on the TiO2 surface and results in an increase of electron injection efficiency. Therefore, the pyrazole-3-carboxylic acid is a promising anchoring group for developing new phthalocyanines to build efficient DSSCs

Synthesis and characterization of poly{2-[3-(1H-pyrrol-2-yl)phenyl]-1H-pyrrole} and its copolymer with EDOT

WOS: 000299519300016A pyrrole-functionalized monomer 2-[3-(1H-pyrrol-2-yl)phenyl]-1H-pyrrole (PyPhPy) was synthesized. The structure of monomer was investigated by Nuclear Magnetic Resonance (H-1 NMR) and Fourier Transform Infrared (FTIR) spectroscopy. The chemical polymerization of PyPhPy (CPyPhPy) was realized using FeCl3 as the oxidant. The electrochemical oxidative polymerization of polymer P(PyPhPy) and its copolymer with 3,4-ethylenedioxythiophene poly(2-[3-(1H-pyrrol-2-yl)phenyl]-1H-pyrrole-co-3,4-ethylenedioxythiophene) [P(PyPhPy-co-EDOT)] were achieved via potentiodynamic method by using NaClO4/LiClO4 as the supporting electrolyte in CH3CN. Characterizations of the resulting polymers were performed by cyclic voltammetry (CV), FTIR, scanning electron microscopy (SEM), UV-Visible spectrophotometry (UV-Vis) and thermogravimetry analyses (TGA). Electrical conductivity of CPyPhPy, P(PyPhPy), and P(PyPhPyco-EDOT) were measured by four-probe technique

Unsymmetrically pyrazole-3-carboxylic acid substituted phthalocyanine-based photoanodes for use in water splitting photoelectrochemical and dye-sensitized solar cells

A new photosensitizer, PCA-ZnPc-2, was synthesized through the asymmetric functionalization of phthalocyanine ring with a pyrazole-3-carboxylic acid as the electron-withdrawing and anchoring group and six hexylsulfanyl as the bulky electron-donating groups. PCA-ZnPc-2 was tested in dye-sensitized solar cells (DSSCs) and its performance was compared with PCA-ZnPc-1. It was found that PCA-ZnPc-2 has higher electron-donating ability which is favorable for light harvesting and suppress the dye aggregation on TiO2 when compared to PCA-ZnPc-1. Also, the new photosensitizer was used in dye-sensitized photoelectrochemical cells for hydrogen production under visible irradiation. The results show that PCA-ZnPc-2 is a promising photosensitizer to harvest the red/near-IR regions