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Lab F
1. A Comprehensive Investigation of Phthalocyanine Metal Cation Complexes J. Canino, J. Head, J. Kasparian, G. Lincourt, A. Mc Cusker, A. Mills, J. Prata University of Rhode Island CHM402 Spring 2007
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3. Phthalocyanines are extremely stable planar molecules with C s symmetry They have an 18 π -electron heterocyclic aromatic system Introduction
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29. Synthesis of Phthalocyanine Reaction 18 -electron aromatic macrocycle Pc can host over 70 different metal ions in its central cavity Metals included in this experiment: Ni Co Mg Cu Li Zn Mn
30. Challenges in Synthesis The central metal is used as a template, activating the bonding of the Phthalonitrile. For efficient synthesis, the central metal must be a particular size. If too large a metal is introduced, the synthesis may not take place. A metal that is too small may fall out of the central hole. 2
31. Large-Scale Synthesis The first phthalocyanine to be manufactured commercially was copper phthalocyanine. It was made in 1934, in England. A similar product was synthesized in the United States in 1937 by Du Pont. Traditional Synthesis Methods: Heating the phthalonitrile to 350-360ºC for 7 hours in a sealed tube, or heating the phthalonitrile to 170-180ºC in triethanolamine for 4 hours. Simply adding 4 moles of phthalonitrile to 1 mole of metal salt at 220-250ºC for 2-6 hours. This procedure would result in a 70-77 percent yield of PC on a plant scale.
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35. Analysis UV-Vis Spectroscopy UV-Vis Spectral range is from 525nm-750nm and it is identify electronic transitions in molecules. Types of Electronic Transitions: Transitions can be metal-to-ligand (MLCT) or ligand-to-metal (LMCT). MLCT are much more common. < 1L/mol-cm d-d spin-forbidden < 10L/mol-cm for Oh or up to 100 L/mol-cm for nearly Oh complexes d-d spin-allowed 1000-10000 L/mol-cm Charge-Transfer Molar absorption coefficient Transition
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40. Group Vibrations of Porphyrins GROUP Frequency (cm -1 ) OH 3590-3610, 3367, 3330 NH 3310-3326, 975-990, 675-700 CH 2976-3077, 2849-2890, 1295, 986 CN 2208-2212 CO 1725-1740, 1640-1668, 905-930, 665
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