Preparation and Electrochemical and Optical Properties of Tetrakis(dithiaselenolo)phthalocyanine

Four o-xylylene groups of phthalocyanine (2) were removed by Birch reduction and the generated octathiolate anions were then reacted with Se to give tetrakis(dithiaselenolo)phthalocyanine (3).The dication generated from 3 in CHCl 3 /TFA was determined with UV-vis and NMR spectroscopy.Phthalocyanines have attracted much attention for their actual and/or potential applications in a variety of fields. 1,2 New types of phthalocyanines have been sought after for developing functional materials, which has stimulated study of the compounds and related areas.][5] We recently reported the preparation of tetrakis(trithiolo)phthalocyanine (PcTTT) by treatment of tetrakis(o-xylylenedithio)phthalocyanine (2) with Li/THF/NH 3 and then with S 8 . 5PcTTT could be protonated with TFA to generate a charged species, which was determined by UV-vis and NMR spectroscopy.If Se atoms could be substituted on the five-membered rings of PcTTT, it would be possible to obtain information regarding the electronic state of the dithiaselenole rings by using the NMR technique.This paper reports the preparation and structure determination of tetrakis(dithiaselenolo)phthalocyanine (3).In addition, the cationic species, generated by treatment of 3 with TFA in CHCl 3 , was examined with UV-vis and NMR spectroscopy.Phthalocyanine (2) was prepared from phthalonitrile (1) by the method previously reported (Scheme 1).5aThe S-C bond of the xylylenedithio groups of 2 could be cleaved by Birch reduction, 4-6 and the generated thiolate anions were functionalized by treatment with Se.