Synthesis and Photophysical, Electrochemical and Theoretical Study of Thi­azole‐Annelated Phthalocyanines

Abstract

Phthalocyanines with annelated thiazole rings were synthesised by cyclotetramerisation of benzothiazoledicarbonitriles. Three types of these dicarbonitriles with ortho‐configuration were prepared from disubstituted anilines and their cyclisation led to all possible patterns of annelation in the phthalocyanine skeleton. Further substitution at the periphery of the macrocycle by methyl or tert‐butyl substituents was realised to improve the solubility or to allow further derivatisation of target molecules. The characteristic UV/Vis spectral Q‐bands were shifted to higher wavelengths (712–729 nm) because of the higher delocalisation, and fluorescence quantum yields increased compared with isoelectronic naphthalocyanines. Aggregation properties of the studied phthalocyanines were dependent on the type of isomer. The effects of the annelation pattern on the redox potentials were also investigated. Experimental data are compared with theoretical values obtained by DFT calculations.

The interaction between a zinc(II) phthalocyanine compound bearing octakis phenoxyacetamide substituents and calf thymus DNA

“…6 In general, weak binding shows no change in absorbance levels. 6,8 The intercalative binding mode of a tiny compound leads to hypochromism with blue shifts or red shifts because of a very powerful arrangement of aromatic parts and DNA base pairs. 18,19 .…”

“…7 The chemical reactivities of phthalocyanine compounds can be changed by altering the peripheral ligands and central metal cations. 8 In addition, phenoxyacetamide-substituted zinc(II) phthalocyanine compounds are biologically effective molecules. A zinc(II) phthalocyanine compound bearing octakis phenoxyacetamide ligands can have potential applications, for example in cancer therapy 9 and in antibacterial 10 treatment.…”

Synthesis, electrochemistry, and electrocatalytic activity of thiazole-substituted phthalocyanine complexes

“…For this purpose, we synthesized new metallophthalocyanines-bearing electropolymerizable thiazole moieties. The studies on the synthesis and electrochemistry of MPcs-bearing thiazole groups are in scare and incorporation redox-active substituents to the Pc are still taking attention to increase the redox richness of similar complexes [21][22][23][24][25][26]. Thus, here synthesis, electrochemistry and spectroelectrochemistry of thiazole-substituted phthalocyanines were examined in detail to illustrate the influence of the thiazole substituents and metal cations and to determine their possible usage in different electrochemical technologies.…”

“…In this study, we investigated the influence of thiazole groups at the periphery and metal ions at the center on the redox activity/inactivity of cobalt (II), manganese (III), iron (III), and zinc (II) phthalocyanines. Existing literature on the synthesis and electrochemistry of MPcs-bearing thiazole groups is scarce and incorporation of redox-active substituents to the periphery still attracts attention to increase the redox richness of similar complexes [21][22][23][24][25][26]. Thus, we here examined in detail the synthesis, electrochemistry, and spectroelectrochemistry of thiazole-substituted phthalocyanines to show the influence of the thiazole substituents and metal cations.…”