Novel Hexadeca-Substituted Metal Free and Zinc(II) Phthalocyanines; Design, Synthesis and Photophysicochemical Properties.

Ayoub Awaji,Shaya Alraqa,Mahmut Durmuş,Ateyatallah Aljuhani,Baybars Köksoy

doi:10.3390/molecules24010077

Ayoub Awaji, Shaya Alraqa + Show 3 more

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https://doi.org/10.3390/molecules24010077

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Abstract

The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine (3a) and its zinc(II) phthalocyanine derivative (3b) have been described and characterized by elemental analysis,1H NMR, 13C NMR, 19F NMR, mass, UV-Vis and FT-IR. The newly prepared metal-free phthalocyanine and its zinc(II) counterpart are soluble in most organic solvents. The photophysical and photochemical properties such as aggregation, fluorescence, singlet oxygen generation and photodegradation under light irradiation of these phthalocyanines have been investigated in DMF. The hexadeca-substituted phthalocyanines (3a and 3b) showed longer absorption and emission wavelength values when compared to that of reported phthalocyanine derivatives due to substitution of the all possible positions in the phthalocyanine framework. The zinc(II) phthalocyanine derivative does not only have a good singlet oxygen generation but also has other photophysicochemical properties that enables this phthalocyanine to be useful as a photosensitizer for cancer treatment using photodynamic therapy.

Highlights

Phthalocyanines (Pcs) are a family of aromatic macrocycles with delocalized 18-π electrons system and are known as useful functional materials due to their high stability and outstanding chemical and physical properties [1]
4-trifluoromethoxyphenyl groups were introduced by the Suzuki-Miyaura coupling reaction, hexyloxy groups were attached to phthalocyanine ring by the Mitsunobu reaction
The novel phthalocyanines were characterized by elemental analysis, 1 H NMR, 13 C NMR, 19 F NMR, mass, UV-Vis and FT-IR

Summary

Introduction

Phthalocyanines (Pcs) are a family of aromatic macrocycles with delocalized 18-π electrons system and are known as useful functional materials due to their high stability and outstanding chemical and physical properties [1] These unique properties have lead them to be used in many applications in different scientific and technological areas such as chemical sensors [2], catalysis [3], liquid crystals [4], photodynamic therapy of cancer [5,6], solar energy conversion [7], nonlinear optics [8], semiconductors [9], and optical data storage [10]. Hexadeca-substituted phthalocyanines are relatively less studied compared to tetra- or octa-substituted counterparts [13,14] These phthalocyanines are useful compounds for PDT [15], catalyst [16], optical materials [17], and Langmuir-Blodgett films [18]. These types of phthalocyanines have become a focus of interest for PDT because of their red-shifted absorptions and Molecules 2019, 24, 77; doi:10.3390/molecules24010077 www.mdpi.com/journal/molecules

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