Ayk BEDUOĞLU and Altuğ Mert SEVİM SYNTHESIS AND CHARACTERIZATION OF NON-SYMMETRICAL METALLOPHTHALOCYANINES AND INVESTIGATION OF THE PHOTOCATALYTIC EFFICIENCY OF THEIR TiO2 COMPOSITES Ayk BEDUOĞLU and Altuğ Mert SEVİM Chemistry Department, Istanbul Technical University, Istanbul *sevim@itu.edu.tr This work was financially supported by the Technological and Scientific Research Council of Turkey with the project number 114R117. In the last 20 years, phthalocyanine chemistry is undergoing a renaissance because phthalocyanines and many of their heterocyclic derivatives exhibit singular and unconventional physical properties interesting for applications in materials science. The phthalocyanine heterocyclic ring has a two dimensional 18π-electron conjugated system and a number of modifications can be made either in the macrocycle by incorporating more than 70 different metal atoms or by inserting side groups at the peripheral sites of the heterocycle. In recent years, there has been a substantial amount of research and development in the area of photocatalytic degradation and heterogeneous photocatalysis. Photocatalytic reactions on TiO2 semiconductors are of great interest because of their applicability to the treatment of a large variety of pollutants. Due to the width of the band gap of TiO2 (3.2 eV), the processes of catalytic oxidative destruction are accomplished upon irradiation with light of the UV region, where only approximately 4% of the solar radiation is effective. The anchoring of pigments, especially phthalocyanine complexes (Pcs), on wideband gap semiconductors is an alternative method to overcome this problem. In this study, two novel non-symmetric zinc(II) and cobalt(II) phthalocyanines with monocarboxylic acid substituents will be synthesized and fully characterized using traditional spectral techniques such as FT-IR, UV-Vis, MALDI-TOF-MS, and 1H-NMR. Then through their interaction with the semiconductor TiO2, TiO2-MPc composites will be prepared and their photocatalytic properties on photodegradation of 4-chlorophenol under visible light have been studied. Figure 2. 1H-NMR spectrum of zinc(II)carboxyphthalocyanine. Figure 3. MALDI-TOF Mass (ZnPc) and UV/Vis spectra of non symmetric carboxy metallophthalocyanines. Figure 1. Synthesis route of targeted non-symmetric carboxyphthalocyanines. Figure 5. Photocatalytic degradation of 4-CP over ZnPc/TiO2 Figure 6. Photocatalytic reusability efficiency of MPc/TiO2 catalysts up to five-cycles. Figure 4. XRD, Diffuse reflectance and FTIR characterization of ZnPc/TiO2 heterogenous catalysts. References: [1] C. C. Lezznoff, A. B. P. Lever, Phthalocyanines Properties and Applications, Vol 1, (1989), Weinheim: VCH. [2] U.I. Gaya, A.H. Abdullah, J. Photochem. Photobiol. C: Photochem. Reviews 9 (2008) 1-12. [3] F. R. F. Fan, A. J. Bard, J. Am. Chem. Soc. 101 (1979) 6139. [4] V. Iliev, J. Photochem. Photobiol. A: Chem. 151 (2002) 195–199. [5] Vallejo, W., Diaz-Uribe C., Cantillo, A. J. Photochem. Photobiol. A: Chemistry (2015) 299, 80-86.