Porphyrazines, or tetraazaporphyrins, are tetrapyrrole macrocycles similar to porphyrins and phthalocyanines. Pioneered by Sir R. Patrick Linstead as an extension of his work on phthalocyanines,[1] porphyrazines differ from porphyrins in that they contain -meso nitrogen atoms, rather than carbon atoms, and differ from phthalocyanines in that their β-pyrrole positions are open for substitution. These differences confer physical properties that are distinct from both porphyrins and phthalocyanines.[2]
Porphyrazines are prepared by magnesium templated cyclization of maleonitriles.[3] Cross-cyclization with phthalonitrile or diiminoisoindole derivatives is possible introducing a flexibile synthetic route that has led to the synthesis of porphyrazines with peripheral heterocyclic rings,[4]heteroatom substituents (S, O, N),[5] peripherally bound metal atoms,[6] and mixed -benzo porphyrazine systems.[7]
Optical propertiesedit
Porphyrazines are most well known for their intense electronic absorption throughout the UV, visible, and NIR spectral regions. Electronic absorption spectra for porphyrazines are similar to those of phthalocyanines,[8] with an intense Soret band (λ ≈ 300 - 400 nm) and Q-band (λ > 600 nm).[7][9]
Porphyrazines exhibit fluorescence from the first excited singlet state (S1 → S0)[10] at visible and NIR wavelengths which is typical of tetrapyrrole macrocycles. Dual-emission from organic fluorophores is not common but, as observed in phthalocyanines,[11][12] violet emission from an upper excited state (S2 → S0) is observed in porphyrazines.[13][14][15]
Referencesedit
^Cook, A. H.; Linstead, R. P., "Phthalocyanines. XI. The preparation of octaphenylporphyrazines from diphenylmaleinitrile." J. Chem. Soc.1937, 929-933.DOI: 10.1039/JR9370000929
^Kobayashi, N. Meso-Azaporphyrins and Their Analogues. In The Porphyrin Handbook, Kadish, K.M.; Smith, K.M.; Guilard, R., Eds.; Academic Press; 1999, Vol. 2, pp. 317-321.
^Angeloni, S.; Ercolani, C., New classes of porphyrazine macrocycles with annulated heterocyclic rings. Journal of Porphyrins and Phthalocyanines, 2000, 4, 474–483.
^For example: Zhao, M; Zhong, C.; Stern, C.; Barrett, A.G.M.; Hoffman, B.M., Synthesis and Properties of Dimetallic M1[Pz]-M2[Schiff Base] Complexes. Inorg. Chem., 2004, 43, 3377-3385.
^ abMiwa, H., Ishii, K., Kobayashi, N., Electronic Structures of Zinc and Palladium Tetraazaporphyrin Derivatives Controlled by Fused Benzo Rings. Chemistry - A European Journal, 2004,10, 4422–4435.
^Kobayashi, N. and H. Konami (1996) Molecular orbitals and electronic spectra of phthalocyanine analogues. In Phthalocyanines: Properties and Applications, Vol. 4 (Edited by C. C. Leznoff and A. B. P. Lever), pp. 343–404. VCH Publishers, Inc., New York.
^Linstead, R. P.; Whalley, M., Conjugated Macrocycles. Part XXI Tetrazaporphin and its Metallic Derivatives. J. Chem. Soc. 1952, 4839-4844.
^Chahraoui, D., Valat, P., and Kossanyi, J., Fluorescence of Phthalocyanines: Emission from an Upper Excited State. Res. Chem. Intermed., 1992, 17, 219-232.
^Kaneko, Y., Nishimura, Y., Takane, N., Arai, T., Sakuragi, H., Kobayashi, N., Matsunaga, D., Pac, C., and Tokumaru, K., Violet emission observed from phthalocyanines. J. Photochem. Photobiol. A, 1997, 106, 177-183.
^Lee, S., White, A.J.P., Williams, D.J., Barrett, A.G.M., and Hoffman, B.M. Synthesis of Near-IR Absorbing/Emitting Porphyrazine Derivatives with Tunable Solubility. J. Org. Chem., 2001, 66, 461-465.
^Lee, S.; Stackow, R.; Foote, C.S.; Barrett, A.G.M.; Hoffman, B.M.; Tuning the Singlet Oxygen Quantum Yield of Near-IR-absorbing Porphyrazines. Photochem. Photobio., 2003, 77, 18-21.
^Trivedi, E.R., Vesper, B.J., Weitman, H., Ehrenberg, B., Barrett, A.G.M., Radosevich, J.A., and Hoffman, B.M., Chiral bis-Acetal Porphyrazines as Near-infrared Optical Agents for Detection and Treatment of Cancer. Photochem. Photobio., 2010, 86, 410-417.
March 17, 2024
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Porphyrazines or tetraazaporphyrins are tetrapyrrole macrocycles similar to porphyrins and phthalocyanines Pioneered by Sir R Patrick Linstead as an extension of his work on phthalocyanines 1 porphyrazines differ from porphyrins in that they contain meso nitrogen atoms rather than carbon atoms and differ from phthalocyanines in that their b pyrrole positions are open for substitution These differences confer physical properties that are distinct from both porphyrins and phthalocyanines 2 Porphyrazine NamesIUPAC name PorphyrazineOther names 5 10 15 20 Tetraazaporphine Tetraazaporphine Tetraazaporphyrin TetrazaporphinIdentifiersCAS Number 500 77 6 Y3D model JSmol Interactive imageChemSpider 24785772PubChem CID 5014177CompTox Dashboard EPA DTXSID70596945InChI InChI 1S C16H10N8 c1 2 10 17 9 1 21 11 3 4 13 18 11 23 15 7 8 16 20 15 24 14 6 5 12 19 14 22 10 h1 8H H2 17 18 19 20 21 22 23 24 Key ZIDZLFREAKMVRI UHFFFAOYSA NSMILES C1 CC3 NC1 NC5 CC C N C2C CC N2 N C4C CC N3 N4 N5PropertiesChemical formula C 16H 10N 8Molar mass 314 312 g mol 1Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox referencesSynthesis editPorphyrazines are prepared by magnesium templated cyclization of maleonitriles 3 Cross cyclization with phthalonitrile or diiminoisoindole derivatives is possible introducing a flexibile synthetic route that has led to the synthesis of porphyrazines with peripheral heterocyclic rings 4 heteroatom substituents S O N 5 peripherally bound metal atoms 6 and mixed benzo porphyrazine systems 7 Optical properties editPorphyrazines are most well known for their intense electronic absorption throughout the UV visible and NIR spectral regions Electronic absorption spectra for porphyrazines are similar to those of phthalocyanines 8 with an intense Soret band l 300 400 nm and Q band l gt 600 nm 7 9 Porphyrazines exhibit fluorescence from the first excited singlet state S1 S0 10 at visible and NIR wavelengths which is typical of tetrapyrrole macrocycles Dual emission from organic fluorophores is not common but as observed in phthalocyanines 11 12 violet emission from an upper excited state S2 S0 is observed in porphyrazines 13 14 15 References edit Cook A H Linstead R P Phthalocyanines XI The preparation of octaphenylporphyrazines from diphenylmaleinitrile J Chem Soc 1937 929 933 DOI 10 1039 JR9370000929 Ghosh A Fitzgerald J Gassman P G Almof J Inorg Chem 1994 33 6057 6060 DOI 10 1021 ic00104a014 Kobayashi N Meso Azaporphyrins and Their Analogues In The Porphyrin Handbook Kadish K M Smith K M Guilard R Eds Academic Press 1999 Vol 2 pp 317 321 Angeloni S Ercolani C New classes of porphyrazine macrocycles with annulated heterocyclic rings Journal of Porphyrins and Phthalocyanines 2000 4 474 483 Michel S L J Hoffman B M Baum S M Barrett A G M Peripherally functionalized porphyrazines Novel metallomacrocycles with broad untapped potential Progress in Inorganic Chemistry 50 473 590 2001 For example Zhao M Zhong C Stern C Barrett A G M Hoffman B M Synthesis and Properties of Dimetallic M1 Pz M2 Schiff Base Complexes Inorg Chem 2004 43 3377 3385 a b Miwa H Ishii K Kobayashi N Electronic Structures of Zinc and Palladium Tetraazaporphyrin Derivatives Controlled by Fused Benzo Rings Chemistry A European Journal 2004 10 4422 4435 Kobayashi N and H Konami 1996 Molecular orbitals and electronic spectra of phthalocyanine analogues In Phthalocyanines Properties and Applications Vol 4 Edited by C C Leznoff and A B P Lever pp 343 404 VCH Publishers Inc New York Linstead R P Whalley M Conjugated Macrocycles Part XXI Tetrazaporphin and its Metallic Derivatives J Chem Soc 1952 4839 4844 Shushkevich I K Pershukevich P P Stupak A P Solov ev K N Journal of Applied Spectroscopy 2005 72 767 770 Chahraoui D Valat P and Kossanyi J Fluorescence of Phthalocyanines Emission from an Upper Excited State Res Chem Intermed 1992 17 219 232 Kaneko Y Nishimura Y Takane N Arai T Sakuragi H Kobayashi N Matsunaga D Pac C and Tokumaru K Violet emission observed from phthalocyanines J Photochem Photobiol A 1997 106 177 183 Lee S White A J P Williams D J Barrett A G M and Hoffman B M Synthesis of Near IR Absorbing Emitting Porphyrazine Derivatives with Tunable Solubility J Org Chem 2001 66 461 465 Lee S Stackow R Foote C S Barrett A G M Hoffman B M Tuning the Singlet Oxygen Quantum Yield of Near IR absorbing Porphyrazines Photochem Photobio 2003 77 18 21 Trivedi E R Vesper B J Weitman H Ehrenberg B Barrett A G M Radosevich J A and Hoffman B M Chiral bis Acetal Porphyrazines as Near infrared Optical Agents for Detection and Treatment of Cancer Photochem Photobio 2010 86 410 417 Retrieved from https en wikipedia org w index php title Porphyrazine amp oldid 999076498, wikipedia, wiki, book, books, library,
