Effects of position (α or β) and linker heteroatom (O or S) of substituent on the photophysicochemical behavior of poly(oxyethylene) substituted ZnPcs and assessment of J-aggregation or protonation using TD-DFT computations

Abstract

A series of zinc phthalocyanines (ZnPcs) tetra-substituted with 1,3-di[2-(2-ethoxyethoxy)ethoxy]-2-propanol (1a) or 1,3-di[2-(2-ethoxyethoxy)ethoxy]-2-propanethiol (1b) at peripheral (β) (6a–b) and non-peripheral (α) (7a–b) positions have been synthesized and characterized. The spectroscopic, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation) properties of these newly synthesized phthalocyanines have been investigated in DMSO. The effects of the position of the substituents on the phthalocyanine skeleton and the nature of the linker heteroatom on their spectroscopic, photophysical and photochemical properties have been determined. The quenching behavior of the zinc phthalocyanines by 1,4-benzoquinone has been studied in DMSO. All of the zinc(II) Pc complexes (6a–b and 7a–b) showed similar electronic absorption spectra in various solvents (chloroform, dichloromethane, DMF, DMSO, THF and toluene). However, complex 7a gave an extra red-shifted band at 742 nm in chloroform and dichloromethane. DFT and TD-DFT computations were performed on the model structures (8a–d, pp-8a–d and 9a–d) to find out the cause of the extra red-shifted Q band (J-type aggregation or protonation of the Pc ring). The computational results showed that monoprotonation of a meso nitrogen atom leads to the formation of this extra band. Photophysical and photochemical measurements indicated that these newly synthesized ZnPc derivatives are promising candidates for use as photosensitizers in the application of PDT.