Synthesis and Characterization of Zn(Tpp) and Cu(Tpp)

Synthesis and Characterization of Zn(TPP) and Cu(TPP) Complexes

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Project Summary The overall goal of the project is to synthesize two metalloporhyrins, (Tetraphenylporphyrinato)zinc(II) and (Tetraphenylporphyrinato)copper(II). Because metalloporphyrins occur naturally in hemoglobin and chlorophyll, their study has implications in synthesizing human blood as well as utilizing its ability to convert visible light to energy. In addition to these two applications, metalloporhyrins are utilized in supramolecular studies, are being researched for potential photodynamic therapy, and are used in building electronics on the molecular scale. While Zinc and Copper may not be the basis of chlorophyll or hemoglobin, by studying any metalloporhyrin, one can gain a greater understanding of the scientific applications surrounding Tetraphenylporphyrin (TPP). In order to generate TPP, the group has elected to use the procedure outlined in Bozak & Hill. This requires adding equal parts of distilled pyrrole and reagent grade benzaldehyde together in a round bottom flask in propionic acid. This solution is then refluxed for about 30 minutes and the precipitate is dried by suction filtration. This product will be analyzed and classified by UV-Vis, FT-IR, and H1 FT-NMR. Once the product is determined to be TPP, it will be reacted with ZnCl2 and CuCl2 separately. An excess amount of the metal chloride will be added to a round bottom flask, along with the TPP, and will be refluxed for 30 minutes in the presence of DMF. The resulting precipitates will then be dried by suction filtration and classified using the same methods as the TPP classification.

Project Description Porphyrin-based compounds and complexes have been studied by experts from a wide range of scientific disciplines, including material science, biomedical science, organic chemistry and supramolecular chemistry. Porphyrin (Figure 1) belongs to the highly symmetrical D4h point group and possesses an extensively conjugated

References: 1. Sakai, H.; Rabbani, M.G.; Hasobe T. Porphyrin hexamer with a triphenylene core unit Spectroscopy, electrochemistry and controllable supramolecular formation. Journal of Porphyrins Phthalocyanines. 2011, 15, 639–651. 2. Olafson, B. D.; Goddard III, W. A. Molecular description of dioxygen bonding in hemoglobin. Proc. Natl. Acad. Sci. USA. 1977, 74, 1315-1319. 3. Khan, S.M.; Kaur, M.; Heflin, J.R.; Sayyad, M.H. Fabrication and characterization of ZnTPP:PCBM bulk heterojunction (BHJ) solar cells. Journal of Physics and Chemistry of Solids. 2011, 72, 1430–1435. 4. Dougherty, T. J.; Henderson, B. W.; Gomer, C. J.; Jori, G.; Kessel, D.; Korbelik, M.; Moan, J.; Peng, Q. Photodynamic therapy. Journ. Nat. Can. Inst. 1998, 90, 889-905. 5. Wormald, R.; Evans, J. R.; Smeeth, L. L.; Henshaw, K. S. Photodynamic therapy for neovascular agerelated macular degeneration. The Cochrane Collaboration. 2009, 6. Regev, A.; Galili, T.; Levanon, H. Effect of Mesophase Structure on the Intermolecular Triplet Quenching of Photoexcited ZnTPP and CuTPP Mixtures. J. Phys. Chem. 1996, 100, 18502-18510. 7. Holten, D.; Bocian, D.F.; Lindsey, J.S. Probing Electronic Communication in Covalently Linked Multiporphyrin Arrays. A Guide to the Rational Design of Molecular Photonic Devices. Acc. Chem. Res. 2002, 35, 57–69. 8. Reid, I.; Zhang, Y.; Dernasi, A.; Blueser, A.; Piper, L.; Downes, J.E.; Matsuura, A.; Hughes, G.; Smith, K.E. Electronic structure of the organic semiconductor copper tetraphenylporphyrin (CuTPP). Applied Surface Science. 2009, 256, 720–725. 9. Yoshimoto, S.; Tada, A.; Suto, K.; Narita, R.; Itaya, K. Adlayer Structure and Electrochemical Reduction of O2 on Self-Organized Arrays of Cobalt and Copper Tetraphenyl Porphines on a Au(111) Surface. Langmuir. 2003, 19, 672-677. 10. Bozak, R. E.; Hill, C. L.; Synthesis of tetraphenylporphin: A convenient undergraduate organic laboratory experiment. J. Chem. Educ., 1982, 59, 36. 12 11. Marsh, D. F.; Mink, L. M. Microscale Synthesis and Electronic Absorption Spectroscopy of Tetraphenylporphyrin H2(TPP) and Metalloporphyrins ZnII(TPP) and NiII(TPP). J. Chem. Ed. 1996, 73, 1188. 12. Xu, C.; Wang, X.; Wang, J.; Hu, H.; Wan, L. Synthesis and photoelectrical properties of β-Cyclodextrin functionalized graphene materials with high bio-recognition capability. Chemical Physics Letters. 2010, 498, 162-7. 13. Rahimi, R.; Gholamrezapor, E.; Naimi-Jamal, M.R.; Rabbani, M. Oxidation of o-chloro and o-hydroxy benzyl alcohols catalyzed by copper (II) tetraphenylporphyrin nanoparticles synthesized by mixed solven method. Current Chemistry Letters. 2012, 1, 101-108. 14. Fagadar-Cosma, G.; Badea, V.; Vlascici, D.; Fagadar-Cosma, E.; Simon, M. Analysis of Some Derivatives of Tetraphenylporphyrin by FT-IR and Mass Spectrometry. 13th Symposium on Analytical and Environmental Problems. Szeged, 25 September 2006. 15. Zhang, Y.; Zhao, W.; Jiang, P.; Zhang, L.; Zhang, T.; Wang, J. Structural parameters and vibrational spectra of a series of zinc meso-phenylporphyrins: a DFT and experimental study. Spectrochimic Acta A Mol Biomol Spectrosc. 2010, 75, 880-890. 16. Hu, S.; Spiro, T.G. The Origin of Infrared Marker Bands of Porphyrin π-Cation Radicals: Infrared Assignments for Cations of Copper(II) Complexes of Octaethylporphine and Tetraphenylporphine. J. Am. Chem. 1993, 115, 12029-34. 17. Dehghani, H.; Mansournia, M.R. Synthesis and Spectroscopic Characterization ofthe New Sitting-atop Complexes from Reaction of Zirconyl Nitrate and Free Base meso-Tetraarylporphyrins in Mild Conditions. Bull. Korean Chem. Soc. 2009, 30, 1715-8. 13