The synthesis and characterization of thyadiazolesubstituted ball-type phthalocyanines

Phthalocyanines, both the synthesis of different derivatives and the use of different application areas are increasing day by day. Ball-type phthalocyanine was first synthesized in 2002 and the number of ball-type phthalocyanine derivatives containing different bridging groups such as arene, naphthalene, coumarin, and pentaerythritol are increasing. The properties of ball- type phthalocyanines such as electrical, electrochemical, spectroelectrochemical, electrocatalytic, gas sensor, photodynamic cancer treatment are studied. 1,3,4-thiadiazole derivatives are used in a wide range of applications such as pharmaceuticals, agriculture and materials chemistry. The synthesis and characterization of the new ball-type metal-free, zinc and ruthenium phthalocyanines containing thiadiazole in the position of bridges will contribute both to the basic sciences and to the preparation of technological materials such as sensors, semiconductors, solar cells, especially in some applications requiring biological activity. In this study, thiadiazole substituted phthalonitrile derivative 1 was synthesized by reaction of 4-nitrophthalonitrile and 1,3,4-thiadiazole-2,5-dithiol in the precense of K2CO3 in DMF. The lithium phthalocyanine derivative was prepared by tetramerization of compound 1 in the presence of Li metal in pentanol, and hydrolysis of this compound with concentrated aceticacid yielded metal-free ball-type phthalocyanine 2. Compound 1 was reacted in DMF with [RuCl2(DMSO)4] or Zn(OAc)2 in the presence of DBU to yield ball-type ruthenium phthalocyanine derivative 3 and ball-type zinc phthalocyanine derivative 4, respectively. The prepared phthalocyanines are dissolved in DMF and DMSO. The novel compounds were characterized by 1H-NMR, 13C-NMR, UV-vis and IR spectroscopy methods.