Synthesis and characterization of new metal-free and metallophthalocyanines containing macrocyclic moieties Halit Kantekin * , Elif C¸ elenk, Hu¨ lya Karadeniz Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey Received 19 November 2007; received in revised form 22 January 2008; accepted 23 January 2008 Available online 2 February 2008 Abstract The synthesis and characterization of new metal-free 7 and metallophthalocyanines 8, 9 carrying macrocyclic N 2 S 2 O 4 donor groups on peripheral positions have been investigated. Phthalonitrile derivative 6 was synthesized according to Rosenmund von Braun proce- dure from compound 5. The novel compounds were characterized by elemental analysis, IR, 1 H and 13 C NMR, UV–Vis and MS spectra data. Ó 2008 Elsevier B.V. All rights reserved. Keywords: Phthalocyanines; Metallophthalocyanine; Macrocyclic compound, mixed-donor macrocyclic 1. Introduction Phthalocyanines and structurally related compounds exhibit properties which are interesting for applications in various fields of material sciences [1]. For example, phthal- ocyanines are used in laser-beam printers and photocopiers [2], in nonlinear optics [3], as liquid crystals [4], as photosen- sitizers [5], in optical data storage [6], as gas sensors [7], as electrochromic substances [8] and as carrier generations materials in near infrared (NIR) [9]. Tetra- and symmetri- cally octasubstituted derivatives are useful compounds in nonlinear optics [10,11] as Langmuir–Blodgett (LB) films [12–16] as well as organic semiconductors. Specificity in the applications of phthalocyanines can be introduced by modification of the phthalocyanine ring or changes in the central metal. Remarkable progress has been made in recent years in the use of phthalocyanine derivatives as sensitizers for photodynamic therapy (PDT) of cancer [17,18]. As the second generation photosensitizers for photodynamic ther- apy (PDT) in the treatment of cancer, phthalocyanines, par- ticularly the aluminum and zinc derivatives, are the most recently studied [19]. By controlling the kinds of central metal ions or introducing appropriate substituents on the phthalocyanine ring, soluble complexes have been pre- pared, and some studies such as redox, photocatalytic, and oxidative catalytic reactions have been reported [20–24]. Macrocyclic ligands containing both nitrogen and sulfur donor atoms are of interest because of their potential for providing molecules capable of mimicking various aspects of macromolecular biological systems. As might be anticipated, the macrocyclic polyamino polythioether ligands exhibit an interesting range of properties intermedi- ate between those of macrocyclic polythioethers and macro- cyclic polyamines [25,26]. We have previously described the synthesis of novel metal-free phthalocyanines and metallophthalocyanines bearing four 27-membered dioxadiazapentathia macrocy- cles moieties on peripheral positions [27]. In the present paper, we have discussed the synthesis, characterization and structural investigation of these novel symmetrical phthalocyanine and its nickel(II) and cobalt(II) derivative. 2. Results and discussion The amine groups of 2,2 0 -(propane-1,3-diylbis(sul- fanediyl))diethanamine (1) were then tosylated in pyridine 0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jorganchem.2008.01.037 * Corresponding author. Fax: +90 0462 325 31 96. E-mail address: halit@ktu.edu.tr (H. Kantekin). www.elsevier.com/locate/jorganchem Available online at www.sciencedirect.com Journal of Organometallic Chemistry 693 (2008) 1353–1358