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

3. Phthalocyanines are extremely stable planar molecules with C s symmetry They have an 18 π -electron heterocyclic aromatic system Introduction

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.

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

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

41. Instrumentation

43. Metal-Free Phthalocyanine

44. Metal Phthalocyanine (Zn)

58. EPR: MgPc

64. 599nm Beer’s Law Plot Ni PC Slope = 2727 L/mol cm

65. 666nm Beer’s Law Plot Ni PC Slope = 3750 L/mol cm

66. 597nm Beer’s Law Plot Co PC Slope = 27547 L/mol cm

67. 657nm Beer’s Law Plot Co PC Slope = 93350 L/mol cm

68. 344nm Beer’s Law Plot Zn PC Slope = 49796 L/mol cm

69. 607nm Beer’s Law Plot Zn PC Slope = 30542 L/mol cm

70. 637nm Beer’s Law Plot Zn PC Slope = 194016 L/mol cm

71. 325nm Beer’s Law Plot Cu PC Slope = 8731L/mol cm

72. 605nm Beer’s Law Plot Cu PC Slope = 3700 L/mol cm

73. 671nm Beer’s Law Plot Cu PC Slope = 11469 L/mol cm