High Photosensitized Singlet Oxygen Generating Zinc and Chloroindium Phthalocyanines Bearing (4‐isopropylbenzyl)oxy Groups as Potential Agents for Photophysicochemical Applications

Abstract

In this study, novel phthalonitrile derivatives (1 and 2) and their peripherally and non‐peripherally tetra (4‐isopropylbenzyl)oxy‐substituted zinc and chloroindium phthalocyanine complexes (3‐6) have been prepared for the first time. The synthesized phthalonitrile derivatives and phthalocyanine complexes were characterized spectroscopically. Not only the chloroindium phthalocyanines but also zinc phthalocyanines are essentially free from aggregation in THF at the studied micromolar concentration. The purpose is to compare the effects of two types of substitution on the phthalocyanines to be used as sensitizers in photodynamic therapy (PDT). Photophysical and photochemical properties of all phthalocyanines are investigated and the results showed that the peripheral phthalocyanines more effectively photooxidize DPBF through singlet oxygen. The photochemical results showed that both ZnPc (3 and 5) and InPc (4 and 6) can be used as sensitizers in PDT because of their very high singlet oxygen quantum yields (range from 0.80 to 0.97).

Effect of Position and Connected Atom on Photophysical and Photochemical Properties of Some Fluorinated Metallophthalocyanines

“…All compounds carrying chloro indium ( 1b , 2b , 3b and 4b ) as the central atom have higher singlet oxygen efficiency than the zinc derivatives ( 1a , 2a , 3a and 4a ) due to the heavy atom effects of larger indium (Table 1). Besides, the complexes 1a and 1b have higher photochemical effects than their respective references (unsubstituted ZnPc (Φ Δ = 0.67) (39) and unsubstituted ClInPc (Φ Δ = 0.61) (48). When comparing 3a and 4b , we observed that the position effect competes with the metal effect.…”

“…The photophysicochemical features of all the stated macromolecules were examined according to the methods described in Refs. (35–39). The related methods and equations have been extensively explained in the "" section.…”

“…Calculation of photodegradation quantum yields was done by performing the method stated in Ref. (39).…”

The Influence of Some Axial Ligands on Ruthenium–Phthalocyanine Complexes: Chemical, Photochemical, and Photobiological Properties

“…Both complexes exhibited sluggish photodegradation kinetics as judged from the unchanged UV-visible spectra in DMSO solution even after irradiation for 40 min. This suggested that the ground-state complex or triplet oxygen might not attack the excited state of the ruthenium-phthalocyanine complexes under irradiation at 660 nm, as opposed to what is generally observed for phthalocyanine derivative complexes (Idowu and Nyokong, 2009;Demirbaş et al, 2019;Güzel et al, 2019). Molecular orbital mixing between phthalocyanine and Ru(II) or (III) might have stabilized the phthalocyanine cycle due to the high activation energy process involving attack by singlet oxygen.…”

Synthesis and Physicochemical Properties of [(1R,2S,5R)-2-isopropyl-5-methylcyclohexyloxy]-thiophen-5-yl-substituted Tetrapyrazinoporphyrazine with Magnesium(II) Ion

“…Singlet oxygen quantum yield was measured in dimethylformamide (DMF) solution under aerobic conditions. It was performed according to a previously described method [42][43][44][45][46]. 1,3-Diphenylisobenzofuran (DPBF) was applied as a singlet oxygen chemical quencher.…”