Bulky 2,6-diphenylphenylsulfanyl substituents efficiently inhibit aggregation in phthalocyanines and tetrapyrazinoporphyrazines and control their photophysical and electrochemical properties

• Published in: Dyes and pigments 2017-01, Vol.136, p.715-723
• Main Authors: Zimcik, Petr, Malkova, Anna, Hruba, Lenka, Miletin, Miroslav, Novakova, Veronika
• Format: Article
• Language: English
• Subjects: Aggregation; Electrochemistry; Fluorescence; Newman-Kwart rearrangement; Phthalocyanine; Singlet oxygen
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2016.09.039

Octasubstituted zinc, metal-free and magnesium complexes of phthalocyanine and tetrapyrazinoporphyrazine bearing very bulky 2,6-diphenylphenylsulfanyl substituents were synthesized. The substituents efficiently inhibited aggregation of the dyes and only monomers were detected even at a concentration of 200 μM solution in toluene. Photophysical data indicated influence of the heavy-atom effect – magnesium complexes were more fluorescent (ΦF 0.40–0.51) and zinc complexes produced stronger the singlet oxygen (ΦΔ 0.56–0.72) in both series of compounds. The presence of additional nitrogens in tetrapyrazinoporphyrazine core made it substantially more electron deficient when compared with corresponding phthalocyanine analogues. 2,6-Diphenylphenylsulfanyl substituents also increased electron deficient character of the core and influenced the photophysical properties. [Display omitted] •2,6-diphenylbenzenethiol was synthesized by Newman-Kwart rearrangement.•Octasubstituted phthalocyanines and tetrapyrazinoporphyrazines were synthesized.•The bulky substituents fully inhibited aggregation in toluene.•2,6-diphenylphenylsulfanyl influenced photophysical and electrochemical properties.