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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
Outline ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Phthalocyanines are extremely stable planar molecules with C s  symmetry They have an 18 π -electron heterocyclic aromatic system Introduction
Introduction ,[object Object],[object Object]
Introduction ,[object Object],[object Object],[object Object],Protoporphyrin IX Heme
Introduction ,[object Object],[object Object],[object Object],[object Object],[object Object],phthalanonitrile
Introduction ,[object Object],4
History ,[object Object],[object Object],[object Object]
History ,[object Object],[object Object],[object Object]
History ,[object Object],[object Object],[object Object]
History ,[object Object],[object Object],[object Object]
History ,[object Object],[object Object],[object Object]
History ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
History ,[object Object],[object Object],[object Object]
History ,[object Object],[object Object]
History ,[object Object],[object Object],Isoindole phthalocyanine
Current Applications   Copper Dyes ,[object Object],[object Object],[object Object],[object Object],[object Object]
Current Applications   Copper Dyes ,[object Object],[object Object],[object Object],[object Object],[object Object]
Current Applications   Copper Dyes ,[object Object],[object Object],[object Object]
Current Applications   CD-R Dyes ,[object Object],[object Object],[object Object],[object Object]
Current Applications   Electrochemistry ,[object Object]
Current Applications   Electrochemistry ,[object Object],[object Object],[object Object]
Current Applications   Thin Film Transistors ,[object Object],[object Object],[object Object],[object Object],[object Object]
Current Applications   Thin Film Transistors ,[object Object],[object Object],[object Object]
Current Applications   Thin Film Transistors ,[object Object],[object Object],[object Object],[object Object]
Current Applications   Catalysis ,[object Object],[object Object],[object Object],[object Object],[object Object]
Current Applications   Catalysis ,[object Object],[object Object],[object Object],[object Object],[object Object]
Synthesis of Phthalocyanine Procedure ,[object Object],[object Object],[object Object],[object Object],[object Object]
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
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
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.
Large-Scale Synthesis Phthalonitrile Processes for industrial yields (90-93% based on phthalonitrile consumed) : ,[object Object],[object Object]
Summary The ideal size for the central metal of the Pc is in the low 70pm ionic radius range. ,[object Object],Improvements: ,[object Object],Analysis: To determine if the desired product was created, an IR, UV-Vis, and EPR was run on each metal Pc.
Analysis: IR Spectroscopy IR region measures the spectrum between the visible and microwave regions.  Practical use ranges from 400-4000cm -1 ,[object Object],[object Object],[object Object],[object Object],[object Object]
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
Analysis: Electron Paramagnetic    Resonance Spectroscopy (EPR) ,[object Object],[object Object],[object Object],μ B  is the Bohr Magneton   9.27401 x 10 -24  J T -1 The g value for a free electron is 2.0023, but the value can differ as a result of spin-orbit coupling.
Analysis: Electron Paramagnetic    Resonance Spectroscopy (EPR) We would not expect to see an EPR in Pc compounds that do not have unpaired electrons.  Compounds that are rather dilute will not exhibit a measurable EPR either. ,[object Object],[object Object]
Infrared Spectroscopy ,[object Object],[object Object],[object Object],[object Object]
Background ,[object Object],[object Object]
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
Instrumentation
[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Instrumentation
Metal-Free Phthalocyanine
Metal Phthalocyanine (Zn)
IR Analysis ,[object Object],[object Object],[object Object],[object Object]
IR of Metal Free Phthalocyanine ,[object Object],[object Object],[object Object],[object Object]
IR Spectral Analysis ,[object Object],[object Object],[object Object],[object Object],[object Object]
EPR: Background ,[object Object],[object Object],[object Object],[object Object],[object Object]
EPR: Theory ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
[object Object],[object Object],EPR:Theory Reference:http://www.chemistry.nmsu.edu/studntres/chem435/Lab7/eprsplit.gif ,[object Object],[object Object]
EPR Theory ,[object Object],[object Object],[object Object],[object Object],[object Object],Reference: http://www.bruker-biospin.com/cwtheory.html
EPR:Theory ,[object Object],[object Object],[object Object],Reference: P. Atkins, T. Overton, “Inorganic Chemistry” 4th edition, W.H. Freeman and Company, New York NY.  2006 , p. 181.
EPR:Theory ,[object Object],[object Object],[object Object],Reference: http://www.bruker-biospin.com/cwtheory.html
EPR:Theory ,[object Object],[object Object],[object Object],[object Object]
EPR:Theory ,[object Object],[object Object],[object Object]
EPR: Applications ,[object Object],[object Object],[object Object],[object Object]
Phthalocyanines & EPR ,[object Object],[object Object]
EPR: MgPc
EPR: Analysis ,[object Object],[object Object],[object Object],[object Object]
EPR: Analysis ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Reference: Moser, Thomas,  Phthalocyanine Compounds,  Reinhold Publishing, New York  1963 , pp49-52. Reference: Assour, J. M., Harrison, S. E.,  Journal of Physical Chemistry , 1964 (68)872-4
EPR:Analysis ,[object Object],[object Object],[object Object],[object Object]
UV/Vis ,[object Object],[object Object],[object Object],M. Gouterman, in  The Porphyrins , ed. D. Dolphin, Academic Press, New York, 1978, vol. III, p.12-17
UV/Vis ,[object Object],[object Object],[object Object],[object Object],[object Object]
599nm Beer’s Law Plot Ni PC Slope = 2727 L/mol cm
666nm   Beer’s Law Plot Ni PC Slope = 3750 L/mol cm
597nm Beer’s Law Plot Co PC Slope = 27547 L/mol cm
657nm Beer’s Law Plot Co PC Slope = 93350 L/mol cm
344nm Beer’s Law Plot Zn PC Slope = 49796 L/mol cm
607nm Beer’s Law Plot Zn PC Slope = 30542 L/mol cm
637nm Beer’s Law Plot Zn PC Slope = 194016 L/mol cm
325nm Beer’s Law Plot Cu PC Slope = 8731L/mol cm
605nm Beer’s Law Plot Cu PC Slope = 3700 L/mol cm
671nm Beer’s Law Plot Cu PC Slope = 11469 L/mol cm
Conclusions ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Conclusions ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Future Applications ,[object Object],[object Object],[object Object],[object Object],[object Object]
Organic Light Emitting Diodes ,[object Object],[object Object],[object Object],[object Object],Image Courtesy and Copyright © 1996-2005  Silicon Chip  Publications Pty Ltd & Web Publications Pty Limited.
Organic Light Emitting Diodes ,[object Object],[object Object],[object Object],[object Object]
Organic Light Emitting Diodes ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
HIV Treatment ,[object Object],[object Object],[object Object],[object Object],[object Object]
HIV Treatment ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
HIV Treatment ,[object Object],[object Object],[object Object],[object Object],[object Object],Compounds were incubated with HIV-1 in a sodium citrate-citric acid buffer of varying pHs for 1 hr. Cells were inoculated and then checked for infected cells 3 days later.
Photodynamic Therapy ,[object Object],[object Object],[object Object],[object Object],[object Object]
Photodynamic Therapy ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Photodynamic Therapy ,[object Object],[object Object],[object Object],[object Object]
Photodynamic Therapy ,[object Object],[object Object],[object Object]
Acknowledgements ,[object Object],[object Object],[object Object]
References ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
References ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]

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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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  • 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
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