Sulfanyl Porphyrazines with Morpholinylethyl Periphery—Synthesis, Electrochemistry, and Photocatalytic Studies after Deposition on Titanium(IV) Oxide P25 Nanoparticles

Abstract

The syntheses, spectral UV–Vis, NMR, and electrochemical as well as photocatalytic properties of novel magnesium(II) and zinc(II) symmetrical sulfanyl porphyrazines with 2-(morpholin-4-yl)ethylsulfanyl peripheral substituents are presented. Both porphyrazine derivatives were synthesized in cyclotetramerization reactions and subsequently embedded on the surface of commercially available P25 titanium(IV) oxide nanoparticles. The obtained macrocyclic compounds were broadly characterized by ESI MS spectrometry, 1D and 2D NMR techniques, UV–Vis spectroscopy, and subjected to electrochemical studies. Both hybrid materials, consisting of porphyrazine derivatives embedded on the titanium(IV) oxide nanoparticles’ surface, were characterized in terms of particle size and distribution. Next, they were subjected to photocatalytic studies with 1,3-diphenylisobenzofuran, a known singlet oxygen quencher. The applicability of the obtained hybrid material consisting of titanium(IV) oxide P25 nanoparticles and magnesium(II) porphyrazine derivative was assessed in photocatalytic studies with selected active pharmaceutical ingredients, such as diclofenac sodium salt and ibuprofen.

Zinc(II) Sulfanyltribenzoporphyrazines with Bulky Peripheral Substituents—Synthesis, Photophysical Characterization, and Potential Photocytotoxicity

“…Another example constitutes a symmetrical zinc(II) sulfanyl porphyrazine with (morpholin-4-yl)ethyl peripheral groups, which was studied in DCM/0.1M TBAP with ferrocene as an internal standard. In this case, the first redox peak was even more positively shifted in comparison to 6 and 7 [37]. However, the absence of aromatic peripheral substituents resulted in a lower electrochemical bandgap, unlike the case of the other macrocycles studied in this paper.…”

Photocatalytic Activity of Sulfanyl Porphyrazine/Titanium Dioxide Nanocomposites in Degradation of Organic Pollutants

“…This paper presents the fabrication, physicochemical characterization, and photocatalytic applications of a hybrid magnesium(II) sulfanyl porphyrazine/TiO 2 nanosystem. This publication is the continuation, and a significant extension of, the preliminary research carried out previously by our group [ 34 ]. It focuses on the physicochemical characterization of the obtained photocatalyst and more advanced studies of the photodegradation of organic compounds—dye, phenolic derivative, and selected drug.…”

Titanium Dioxide-Based Photocatalysts for Degradation of Emerging Contaminants including Pharmaceutical Pollutants

“…In our latest study, metallic porphyrazines (Mg and Zn) functionalized with morpholinylethylsulfanyl moieties were used to functionalize P25 TiO 2 . Novel hybrid material was subsequently applied in photocatalytic studies with active pharmaceuticals such as diclofenac sodium salt and ibuprofen, dissolved in organic solvents [165]. The employed functional groups promoted agglomeration of the hybrid nanoparticles by a large margin (the mean diameter increased over four times compared to pure P25).…”

“…Based on these results, the magnesium porphyrazine was chosen for further photocatalytic tests with diclofenac sodium salt and ibuprofen. The hybrid material was photocatalytically active and degradation of both substances was noted after irradiation with red light for 8 min [165]. In another study with nipagin-functionalized porphyrazines, phthalocyanines, and P25 TiO 2 , fluorescence and singlet oxygen quantum yields as well as photostability were assessed [166].…”