The synthesis and characterization of new metal-free and metallophthalocyanines containing four 27-membered diazaheptathia macrocycles H. Zeki Go ¨k a , Halit Kantekin a, * , Yas xar Go ¨k a , Gerrit Herman b a Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey b Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S.3), B-9000 Gent, Belgium Received 23 June 2006; received in revised form 29 June 2006; accepted 2 July 2006 Available online 1 September 2006 Abstract A new metal-free 5 and metallophthalocyanines 6 and 7 containing four 27-membered diazaheptathia macrocyclic moieties on peripheral positions have been synthesized. The metal-free phthalocyanine 5 was synthesized by the reaction 27,28-dicyano-9,10,12,13,23,24,31,32- octahydro-5H,15H-tribenzo[b,h,w][1,4,7,13,16,19,25,10,22]heptathia diazacycloheptacosine-6,16 (7H,17H )-dione 4 with anhydrous 2-(dime- thylamino)ethanol under reflux for 28 h. Metallophthalocyanines 6 and 7 were synthesized by the reaction of 4 with anhydrous NiCl 2 and Zn(CH 3 CO) 2 in dry quinoline, respectively. The new compounds were characterized by a combination of elemental analysis and 1 H NMR, 13 C NMR, IR, UVevis and MS spectral data. Ó 2006 Elsevier Ltd. All rights reserved. Keywords: 2-Aminothiophenol; Mixed-donor macrocycle; Phthalocyanines; Template effect; Transition metal 1. Introduction Phthalocyanine, which was first developed as a pigment, has found widespread applications in materials science [1]. It has been employed as charge carriers in photocopiers and laser printers, as well as materials for optical storage in recent years [2,3]. Many potential applications are expected for these molecular materials which have a high thermal and chemical stability, for instance oxidation catalysis [4], solar cell func- tional materials [5], gas sensors [6], nonlinear optical limiting devices [7], photodynamic therapy agents [8], antimycotic ma- terial [9], and corrosion inhibitors [10], infectious diseases [11], and eye and neurodegenerative diseases [12]. The elec- trochemical and spectroscopic properties can be altered by changing the metal center. The other way to tune the proper- ties of phthalocyanine compounds is to introduce different kinds of substituents onto the peripheral and nonperipheral po- sitions of the phthalocyanine ring. Particularly, the optical and electrochemical properties of phthalocyanines can be signifi- cantly altered by incorporating substituents at the nonperiph- eral positions. Because of their potential applications, tens of thousands of tons of phthalocyanines (Pcs) are produced per year worldwide [13]. In the last few decades the synthesis of artificial receptors that are able to coordinate metal cations undergone a spectac- ular growth [14,15]. Most of the attention has been focused on macrocyclic receptors capable to bind more than one transition metal ion [16e22]. Depending on the nature of subunits used for their construction, a variety of macropolycyclic structures have been synthesized. Most of these ligands contain both ni- trogen and oxygen donor atoms and have a great affinity for alkali-metal and alkaline-earth metal cations. To enhance the coordinating properties of these macrocycles, different modifi- cations have been made such as the ring size, the nature of substituents, and the type of donor atoms [23]. There are only a few reports concerning the Ag þ complexabilities and * Corresponding author. Tel.: þ90 462 377 2589; fax: þ90 462 325 3196. E-mail address: halit@ktu.edu.tr (H. Kantekin). 0143-7208/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.dyepig.2006.07.008 Dyes and Pigments 75 (2007) 606e611 www.elsevier.com/locate/dyepig