Synthesis and characterization of poly¯uoroalkoxysulfonyl phthalonitriles and corresponding zinc and cobalt phthalocyanines Natalya V. Kondratenko a , Irina N. Tretyakova b , Eugene A. Luk'yanets c , Sergey V. Volkov b , Raisa K. Orlova a , Victor N. Nemykin b , Lev M. Yagupolskii a, * a Institute of Organic Chemistry, 5 Murmanskaya, 253660, Kiev, Ukraine b Institute of General and Inorganic Chemistry, 32/34 Palladina Ave, 252680 Kiev 142, Ukraine c Organic Intermediates and Dyes Institute, 1/4 B.Sadovaya, 103787 Moscow, Russia Received 6 July 1998; accepted 27 July 1998 Abstract The reaction of 1,2-dicyanobenzene-4-sulfonyl chloride with dierent poly¯uoro alcohols leads to the formation of 1,2-dicyano-4-poly¯uoroalkoxysulfonyl benzenes. The tetramerization of such nitriles in the presence of zinc or cobalt salts results in the corresponding phthalocyanines. The in¯uence of solvent and substituents on the aggregation of the phthalocyanine complexes was studied by electronic spectroscopy. The poly¯uoroalkoxysulfonyl groups were shown to stabilize both HOMO and LUMO of the complexes in comparison with alkoxy- or poly¯uoroalkoxy-substituted ana- logs. The ®rst oxidation potential for zinc-containing complexes was estimated as 1.47±1.65 V # 1999 Elsevier Science Ltd. All rights reserved. Keywords: Fluorinated phthalonitriles; Substituted phthalocyanine complexes; Aggregation 1. Introduction Phthalocyanines are traditionally used as dyes and pigments [1]. Recently their uses have been developed in the context of passive quality switches in lasers, as catalysts, semiconductors and photosensitizers for the photodynamic therapy of cancer [2]. Redox-active d-metal (Mn, Fe, Co) phthalocyanine complexes exhibit very high cata- lytic activity in the oxidation reactions of thiols, hydrocarbons, hydroquinones, arenes, and amines [3±5]. The oxidation of the phthalocyanine ligand is the main inactivation pathway for such catalysts. Thus, the synthesis of novel phthalocyanine com- plexes with high oxidation potential of macrocyclic ligands can lead to new highly eective catalytic systems. The most promising way to increase the ®rst oxidation potential of phthalocyanine ligands is the introduction of electron-withdrawing sub- stituents. Recently, high peroxidase and oxygenase activities were observed in transition-metal Dyes and Pigments 41 (1999) 101±109 0143-7208/99/$Ðsee front matter # 1999 Elsevier Science Ltd. All rights reserved. PII: S0143-7208(98)00066-7 * Corresponding author. Tel.: +380-44-551-0652; fax: +380- 44-573-2643.