A new type peripherally and nonperipherally thiazol substituted soluable phthalocyanines

Metal-free phthalocyanine (H2Pc) was obtained by accident for the first time in 1907 as a by-product during the preparation of 2-cyanobemzamide. Twenty years after this discovery, copper phthalocyanine was synthesized by Disbach and his coworker from 1,2-dibromobenzene in 1927. Linstead and his coworkers prepared several metallophthalocyanines (MPc) by developing synthetic methods and elucidated the structure of phthalocyanines (Pcs). X-ray diffraction analyses of them were performed by Robertson. The name phthalocyanine was first used by Linstead. Pcs are synthetic macrocycles structurally similar to naturally available porphyrins such as hemoglobin, chlorophyll, and vitamin B12. They can be regarded as tetrabenzotetraazaporphyrins and as tetramerezitation products of 4 iso-indoline units and consist of a planar structure with an 18 π-electron system. They are very stable blue or green pigments and dyes, an important class of chemicals for commercial use in many areas of technology. As a blue pigment CuPc was first produced industrially in 1935 by an English company and then other companies in Germany and the USA. Today, CuPc and peripherally or nonperipherally substituted derivatives, and about 70 different elements including metals and some metalloids have been used as central atoms in all kinds of Pcs [1]. Phthalocyanines have found a great number of important technological applications such as in non-linear opticdevices, dyes and pigments, catalysts, medical applications, chemical sensors, electrochromic devices and liquid crystals. In medicine, phthalocyanines have been found to have applications as phototoxic drugs for photodynamic therapy of cancer. Aromatic heterocyclic compounds containing nitrogen and sulfur have important industrial uses. Thiazole, a five-membered ring heterocycle, is an important species of this type and enjoys widespread use for manufacturing biocides, fungicides, dyes and pharmaceuticals, treatment of inflammation, hypertension, bacterial and HIV infections. It is a liquid which smells like pyridine and the boiling point is 117°C. The molecules is considerably stable, on the other hand it is very weak as a base. It is the natural ring ve it is the functional group of the thiamine (B1 vitamin) and epothilone, a potent anti-cancer drug. There is a thiazole ring in the penicillin structure. If the quintet ring is the place 1,3, the structure name is "thiazole", if the quintet ring is the place 1,2, the structure name is iso-thiazole. In general, thiazoles are well represented in biomolecules. Thiazoles are characterized by a larger delocalisation of the p-electrons than that obtained for the corresponding oxazoles and, therefore, possess superior aromatic character. The thiazole derivatives exhibit a wide range of importantbiological activities, including drugs in pharmaceutical industry; because of this reason we have planned to make an attempt toattach thiazole groups onto the Pc ring. Within the scope of the thesis, the new type metalo phthalocyanines were prepared with the substituted thiazole groups which are providing solubility and with the different metal salts. Electrochemical speciality and redox behaviours is evaluated of the catalytic reduction of hydrogen for the new synthesized phthalocyanines complexes of were tried to defined electrocatalytic activities and including Co, Zn, Mn active metals that are redox active materials which are active, different and suitable for the aim of usage and has the multiple reversible electron transfer speciality were synthesized. Firstly, the new new synthesized phthalocyanines were defined electrochemical, spectrochemical and thin film specialities for being investigated of the electrocatalitic activities. In this way, it is planned that more productive and utilizable hydrogen production system modelling can be realized. For this aim, first part of the studying the novel, symmetrical, nonperipherally tetrasubstituted metallophthalocyanines (cobalt, zinc, and manganese) bearing four 2-(4-methyl-1,3-thiazol-5-yl)ethoxy units were synthesized. Therefore, cyclotetramerizations of the dicyano-derivative (3) to the metallo-phthalocyanines (6-8) were accomplished in n-hexanol in the presence of DBU and metal salts (CoCl2, Zn(CH3COO)2, MnCl2). Elemental analyses and spectral data (EI-MS, MALDI-TOF, 1H-NMR, UV-Vis, and FT-IR) for all new products are consistent with the proposed structures. Photophysical properties with zinc (II) (7) phthalocyanine were found, including electronic absorption and fluorescence quantum yield. The fluorescence of the complexes was investigated in DMF and it was found that benzoquinone (BQ) was an effective quencher. The response and recovery behaviours of the spin coated films to different analytes, which span a broad range of Lewis base, have been investigated by means of conductivity measurements. It was observed that the operating temperature had a considerable effect on the gas sensing performance of the sensors investigated. The sensing behaviour of the films for a broad range of Lewis bases and the correlation between the sensor sensitivity and Lewis base enthalpies were investigated. Results show that sensitivity of the films may be correlated exponentially with binding enthalpy. In the second part of this study, the novel, symmetrical, peripherally octasubstituted metallophthalocyanines (cobalt, zinc, and manganese) bearing 2-(4-methyl-1,3-thiazol-5-yl)etoksi]ftalonitril) units were synthesized. Therefore, cyclotetramerizations of the dicyano-derivative (5) to the metallo-phthalocyanines (9-11) were accomplished in n-hexanol in the presence of DBU and metal salts (CoCl2, Zn(CH3COO)2, MnCl2). Elemental analyses and spectral data (EI-MS, MALDI-TOF, 1H-NMR, UV-Vis, and FT-IR) for all new products are consistent with the proposed structures. Aggregation behaviors of phthalocyanines were investigated in different solvents. Redox properties of the complexes were determined with voltammetric and in situ spectroelectrochemical measurements. The Beer– Lambert law was obeyed for the compounds in DMF for the concentrations ranging from 4.00x10-6 to 14.00x10-6 M. Electrochemical and spectroelectrochemical measurements exhibit that the incorporation of the redox-active metal ions, CoII and MnIIIOAc, into the phthalocyanine core extends the redox richness of the Pc ring with the reversible metal-based reduction and oxidation couples in addition to the common Pc ring-based electron transfer processes. Assignments of the redox processes of the complexes were supported with in situ spectroelectrochemical measurements. Multi-electron and metal and Pc based redox properties of the complexes increase the worth of the complexes for the possible use as functional materials in various electrochemical applications, such as the fields of electrosensing, electrochromism, and electrocatalysis.