Synthesis and Photophysical, Electrochemical and Theoretical Study of Thi­azole‐Annelated Phthalocyanines. Issue 32 (1st October 2015)

• Record Type: Journal Article
• Authors: Nečedová, Mária; Magdolen, Peter; Novakova, Veronika; Cigáň, Marek; Vlčková, Silvia; Zahradník, Pavol; Fülöpová, Andrea
• Is Part Of: European journal of organic chemistry. Issue 32(2015)
• Page Start: 7053
• Page End: 7068
• Publication Date: 2015-10-01
• Subjects: Phthalocyanines -- Benzothiazole -- Electrochemistry -- Aggregation -- Density functional calculations; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201500785
• Languages: English
• ISSNs: 1434-193X

Abstract

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. Abstract : To elucidate the effect of annelation of thiazole rings onto the phthalocyanine macrocyclic system, the photophysical and photochemical properties of a series of regioisomers were investigated. The properties and behaviour of the derivatives were compared with their well‐known phthalocyanine analogues. The observed characteristics were consistent with those predicted by DFT calculations.