Yeni Tip Ftalosiyaninlerin Sentezi

Sibel Eken Korkut

Yeni Tip Ftalosiyaninlerin Sentezi

Thesis Type: Doctorate

Institution Of The Thesis: Yildiz Technical University, Faculty of Arts & Science, Department of Chemistry, Turkey

Approval Date: 2013

Thesis Language: Turkish

Student: Sibel Eken Korkut

Supervisor: Muhammet Kasım Şener

Open Archive Collection: AVESIS Open Access Collection

Abstract:

Phthalocyanines are macroheterocyclic compounds which comprise of four isoindole units linked by nitrogen atoms at the meso position. Phthalocynanines are usually synthesized starting from the appropriate phthalonitriles and their derivatives (ex.: phthalimide, phthalicacid, etc.) or their substitution yield as metal-free phthalocyanine and metallophthalocyanines which are obtained especially in high temperatures in the presence of a suitable anhydrous metal salt. Phthalocyanines that are completely synthetic materials are used in energy transfer, electrophotography, optic data collection, gas sensor, liquid crystal, infrared dye for lazer technology, one-dimensional metals as well as dyes and pigments. In the first part of this study; we have made use of the potential for exchanging the acidic ?CH proton of dimethylmalonate with the nitro group of 3-nitrophthalonitrile and dimethyl-(2,3-dicyanophenyl) malonate (1) compound and its phtalocyanine derivatives. For this purpose, 3-nitrophthalonitrile was treated with malonic acid dimethyl ester in the presence of K2CO3 in anhydrous DMF and the phthalonitrile derivative dimethyl-(2,3-dicyanophenyl) malonate (1) was obtained. The synthesis of phthalocyanine derivatives of phthalonitrile compound is usually done in the presence of an N-donor base (ex.: DBU, pridyne) in solvents with high boiling points (ex.: n-penthanol, n-hexanol). The metallophthalocyanines with Cu(II), Co(II) and Pd(II) (2-4) were synthesized in n-hexanol in the presence of DBU and the appropriate metal salt, at 160 0C. Reaction was carried out for 24 hours. The basicity of DBU was sufficient to carry out transesterification, so that methyl groups in the precursor (1) were converted into hexyl groups during phthalocyanine formation in hexanol. In order to preserve dimethylester functionality after phthalocyanine formation, the reaction was carried without using any solvent. However, all efforts to accomplish this reaction failed. The most obvious feature of the newly synthesized metallophthalocyanines is their high solubility in common organic solvents, for example, ethanol, methanol, chloroform, dichloromethane, acetone, and tetrahydrofuran. In compound 1, stretching vibrations of C?N (2233 cm-1), C=O (1758 cm-1 and 1743 cm-1), C?O?C (1197 cm-1- 1145 cm-1) appeared at expected frequencies. CH stretching vibrations are observed 2958 cm-1 and aromatic CH stretching vibrations are observed 3085 cm-1- 3030 cm-1. The IR spectrum of 1 and those of 2, 3, 4 were similar, the only difference being the disappearence of C?N vibration in the latter group. In the 1H NMR spectrum of 1, the aromatic protons appear at 8,05-8,03 ppm and 7,86-7,78 ppm. CH and CH3 protons are observed 5,21 and 3,84 ppm. EI-MS spectrum of 1 the [M+Na]+ peak appeared at m/z 281,03 amu 1H NMR investigations of compound 3 provided the characteristic chemical shifts for the structures expected. 1H-NMR investigation of 3 provided the characteristic chemical shifts for the structure expected. The 1H-NMR spectrum of 3 is somewhat broader than the corresponding signals in the dinitrile derivative 1. The mass spectra of 2 and 3 were obtained by MALDI technique. MALDI TOF mass spectrum of 2, in addition to the [M+Na+K]+ peak at 1719,21, fragment ions such as [M-COOC6H13+Na+K]+ at 1591,23, [M-2(COOC6H13)+2Na]+ at 1444,12, [M-3(COOC6H13)+2Na]+ at 1315,01, were easily identified. In the case of 3, we observed an [M]+ peak at 1699,85 and the other ions such as [M-COOC6H13+3H]+ at 1573,44, [M-2(COOC6H13)+2H]+ at 1443,12, [M-3(COOC6H13)+4H]+at 1316,96. UV-Vis spectra of all metallophthalocyanines 2-4 in chloroform exhibit intense Q bands around 663?683nm and the characteristic band of phthalocyanines, B bands in the near UV region, around 331?341 nm. In the second part of this work, zinc and cobalt phthalocyanines with electroactive and electropolymerizable EDOT's at peripheral positions were synthesized and their electrochemical, spectroelectrochemical, and electrocolorimetric properties were studied. Electropolymerizations were also carried out. 4-((2,3-Dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy)phthalonitrile (5) was prepared by a base-catalyzed nucleophilic aromatic displacement of 4-nitrophthalonitrile with hydroxymethyl-EDOT. The reaction was carried out at room temperature in dry dimethylformamide with K2CO3 for 96 hours. Cyclotetramerization of the dinitrile compound 5 in the presence of anhydrous metal salts gave the desired metallophthalocyanines of Zn(II) and Co(II) (6, 7). In compound 5, stretching vibrations of C?N (2227 cm-1) appeared at expected frequencies. The CH stretching vibrations arising from aliphatic groups appeared at 2933 cm-1. 1H NMR spectrum of 1, exhibited the aromatic protons, integrating for a total of 5, at 7,68?7,16 ppm and 6,32 ppm. Also CH and CH2 protons of 5 were observed at 4,53 ppm and 4,25 ppm which integrated for 5 protons. 13C NMR data of 5 confirm the result of the 1H NMR spectrum. In the ESI-MS spectrum of 5, we observed the [M+H]+ peak at m/z 299,04 amu. The IR spectra of phthalocyanines confirmed the formation of the metallophthalocyanines (6, 7) via cyclotetramerization of dinitrile compound, due to disappearance of the sharp triple bond signal seen in 5 at 2227 cm?1. In the MALDI-TOF mass spectrum, we observed a [M+H]+ peak at 1259,33 for 6 and a [M]+ peak at 1252,58 for 7. UV?vis spectra of all metallophthalocyanines 6, 7 in DMSO exhibit intense Q bands around 664?680 nm and the B bands in the near UV region, around 337?356 nm. For the last part of this work; a novel dinitrile compound 8 which is a type II photoinitiator and a zinc phthalocyanine derivative were prepared and characterized. Photoinitiated polymerization of methyl methacrylate with 9 has been investigated in the presence and absence of a co-initiator. Fluorescence and phosphorescence measurements have been also performed to determine the photophysical properties. Low fluorescence quantum yield (?"F" = 0,08) compare to the unsubstituted ZnPc has been found. This allows initiator to undergo intersystem crossing into the triplet state. 4-(9-oxo-9H-thioxanthen-2yloxy)phthalonitrile (8) was obtained through the reaction of 4-nitrophthalonitrile and 2-hydroxythioxanthone at room temperature in the presence of K2CO3 in dry dimethylformamide. The metallophthalocyanine (9) was obtained through the reaction of the dinitrile compound (8) and the appropriate metal salt in n-hexanol at 160 0C and argon atmosphere for 24 hours. As a naturel consequence of the single substituent on each benzo group, the zinc phthalocyanine is a mixture of four constitutional isomers. IR spectrum of 8 indicated the presence of aromatic, C?N and C=O groups by the intense stretching bands at 3066, 2232 and 1637 cm-1, respectively. 1H NMR spectrum of 8, exhibited the aromatic protons, integrating for a total of 10, at 8,66-7,23 ppm. 13C NMR data of 8 confirm the result of the 1H NMR spectrum. In the GC-MS spectrum of 8, we observed the [M]+ peak at m/z 354 amu. The IR spectra of zinc phthalocyanine confirmed the formation of the macrocycle, due to disappearance of the sharp triple bond signal seen in 8 at 2232 cm-1. 1H NMR investigation of compound 9 provided the characteristic chemical shifts for the structure expected. The 1H NMR spectrum of 9 is somewhat broader than the corresponding signals in the dinitrile derivative 8. In the MALDI-TOF mass spectrum, we observed a [M+H]+ peak at 1483,91 amu for 9. The steady-state absorption spectra of 9 in DMF exhibit intense Q band at 674 nm and the B band in the near UV region, at 348 nm, both correlated to ?-?* transitions.