Tetraphenylporphyrin

Tetraphenylporphyrin, abbreviated TPP or H2TPP, is a synthetic heterocyclic compound that resembles naturally occurring porphyrins. Porphyrins are dyes and cofactors found in hemoglobin and cytochromes and are related to chlorophyll and vitamin B12. The study of naturally occurring porphyrins is complicated by their low symmetry and the presence of polar substituents. Tetraphenylporphyrin is hydrophobic, symmetrically substituted, and easily synthesized. The compound is a dark purple solid that dissolves in nonpolar organic solvents such as chloroform and benzene.

Tetraphenylporphyrin
Lewis structure for meso-tetraphenylporphyrin
Ball-and-stick model of the tetraphenylporphyrin molecule
Names
IUPAC name
5,10,15,20-Tetraphenyl-21H,23H-porphyrin
Systematic IUPAC name
[12(2)Z,15(8)Z,35(4)Z,6(72)Z]-2,4,6,8-Tetraphenyl-11H,51H-1,3,5,7(2,5)-tetrapyrrolacyclooctaphane-12(2),15(8),35(4),6(72)-tetraene
Other names
5,10,15,20-Tetraphenylporphin, TPP, H2TPP
Identifiers
3D model (JSmol)
379542
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.011.842
MeSH C509964
UNII
  • InChI=1S/C44H30N4/c1-5-13-29(14-6-1)41-33-21-23-35(45-33)42(30-15-7-2-8-16-30)37-25-27-39(47-37)44(32-19-11-4-12-20-32)40-28-26-38(48-40)43(31-17-9-3-10-18-31)36-24-22-34(41)46-36/h1-28,45,48H/b41-33-,41-34-,42-35-,42-37-,43-36-,43-38-,44-39-,44-40- ☒N
    Key: YNHJECZULSZAQK-LWQDQPMZSA-N ☒N
  • InChI=1/C44H30N4/c1-5-13-29(14-6-1)41-33-21-23-35(45-33)42(30-15-7-2-8-16-30)37-25-27-39(47-37)44(32-19-11-4-12-20-32)40-28-26-38(48-40)43(31-17-9-3-10-18-31)36-24-22-34(41)46-36/h1-28,45,48H/b41-33-,41-34-,42-35-,42-37-,43-36-,43-38-,44-39-,44-40-
    Key: YNHJECZULSZAQK-LWQDQPMZBQ
  • C=9C=CC(C7=C1C=CC(=N1)C(C=2C=CC=CC=2)=C3C=CC(N3)=C(C=4C=CC=CC=4)C=5C=CC(N=5)=C(C=6C=CC=CC=6)C8=CC=C7N8)=CC=9
Properties
C44H30N4
Molar mass 614.74 g/mol
Appearance dark purple solid
Density 1.27 g/cm3
insoluble in water
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H302, H312, H332
P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P312, P322, P330, P363, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
Infobox references

Synthesis and structure

Tetraphenylporphyrin was first synthesized in 1935 by Rothemund, who caused benzaldehyde and pyrrole to react in a sealed bomb at 150 °C for 24 h.[1] Adler and Longo modified the Rothemund method by allowing benzaldehyde and pyrrole to react for 30 min in refluxing propionic acid (141 °C) open to the air:[2]

8 C4H4NH + 8 C6H5CHO + 3 O2 → 2 (C6H5C)4(C4H2N)2(C4H2NH)2 + 14 H2O

Despite its modest yields, the synthesis of H2TPP is a common experiment in university teaching labs.[3][4] Highly efficient routes to H2TPP and many analogues involve the air-free condensation of the pyrrole and aldehyde to give the porphyrinogen. In this so-called Lindsey synthesis of meso-substituted porphyrins, the porphyrinogen is subsequently oxidized to deliver the porphyrin.[5]

The conjugate base of the porphyrin, TPP2−, belongs to the symmetry group D4h while its hydrogenated counterpart H2(TPP) is D2h. Unlike natural porphyrins, H2TPP is substituted at the oxidatively sensitive "meso" carbon positions, and hence the compound is sometimes called meso-tetraphenylporphyrin. Another synthetic porphyrin, octaethylporphyrin (H2OEP) does have a substitution pattern that is biomimetic. Many derivatives of TPP and OEP are known, including those prepared from substituted benzaldehydes. One of the first functional analogues of myoglobin was the ferrous derivative of the "picket fence porphyrin," which is structurally related to Fe(TPP), being derived via the condensation of 2-nitrobenzaldehyde and pyrrole.

  • Metal-TPP Complexes
  • A picket-fence porphyrin complex of Fe, with axial coordination sites occupied by methylimidazole (green) and dioxygen (R = amide groups).
    A picket-fence porphyrin complex of Fe, with axial coordination sites occupied by methylimidazole (green) and dioxygen (R = amide groups).[6]
  • Structure of Fe(TPP)CC(C6H4Cl)2, one of several iron carbenoid complexes reported by Daniel Mansuy.
    Structure of Fe(TPP)CC(C6H4Cl)2, one of several iron carbenoid complexes reported by Daniel Mansuy.[7]

Sulfonated derivatives of TPP are also well known to give water-soluble derivatives, e.g. tetraphenylporphine sulfonate:

4 SO3 + (C6H5C)4(C4H2N)2(C4H2NH)2

→ (HO3SC6H4C)4(C4H2N)2(C4H2NH)2 + 4 H2O

Complexes
Main article: Transition metal porphyrin complexes

Complexation can be thought of as proceeding via the conversion of H2TPP to TPP2−, with 4-fold symmetry. The metal insertion process proceeds via several steps, not via the dianion. Representative complexes:

Optical properties
Optical properties of tetraphenylporphyrin in toluene

Tetraphenylporphyrin has a strong absorption band with maximum at 419 nm (so called Soret band) and four weak bands with maxima at 515, 550, 593 and 649 nm (so called Q-bands). It shows red fluorescence with maxima at 649 and 717 nm. The quantum yield is 11%.[11] Soret red shifts for Zn(TTP)-Donor systems relative to the Soret band at 416.2 nm for Zn(TTP) in cyclohexane have been measured.[9]

Applications
Hydrogen can be removed from individual H2TPP molecules by applying excess voltage to the tip of a scanning tunneling microscope (a); this removal alters the I-V curves of TPP from diode like (red curve in b) to resistor like (green curve). Image (c) shows a row of TPP, H2TPP and TPP molecules. While scanning image (d), excess voltage was applied to H2TPP at the black dot, which instantly removed hydrogen, as shown in the bottom part of (d) and in the re-scan image (e).[12]

H2TPP is a photosensitizer for the production of singlet oxygen.[13] Its molecules have potential applications in single-molecule electronics, as they show diode-like behavior that can be altered for each individual molecule.[12]

References
  1. P. Rothemund (1936). "A New Porphyrin Synthesis. The Synthesis of Porphin". J. Am. Chem. Soc. 58 (4): 625–627. doi:10.1021/ja01295a027.
  2. A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour and L. Korsakoff (1967). "A simplified synthesis for meso-tetraphenylporphine". J. Org. Chem. 32 (2): 476. doi:10.1021/jo01288a053.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  3. Falvo, RaeAnne E.; Mink, Larry M.; Marsh, Diane F. (1999). "Microscale Synthesis and 1H NMR Analysis of Tetraphenylporphyrins". J. Chem. Educ. 1999 (76): 237. Bibcode:1999JChEd..76..237M. doi:10.1021/ed076p237.
  4. G. S. Girolami, T. B. Rauchfuss and R. J. Angelici (1999) Synthesis and Technique in Inorganic Chemistry, University Science Books: Mill Valley, CA.ISBN 0935702482
  5. Lindsey, Jonathan S. (2000). "Synthesis of meso-substituted porphyrins". In Kadish, Karl M.; Smith, Kevin M.; Guilard, Roger (eds.). Porphyrin Handbook. Vol. 1. pp. 45–118. ISBN 0-12-393200-9.
  6. S. J. Lippard, J. M. Berg “Principles of Bioinorganic Chemistry” University Science Books: Mill Valley, CA; 1994. ISBN 0-935702-73-3.
  7. Mansuy, Daniel; Battioni, Jean Paul; Lavallee, David K.; Fischer, Jean; Weiss, Raymond (1988). "Nature of the complexes derived from the reaction of 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (DDT) with iron porphyrins: Crystal and molecular structure of the vinylidene carbene complex Fe(TPP)(C:C(p-ClC6H4)2)". Inorganic Chemistry. 27 (6): 1052–1056. doi:10.1021/ic00279a023.
  8. R. F. Pasternack, G. C. Vogel, C. A. Skowronek, R. K. Harries and J. G. Miller (1981). "Copper(II) Incorporation into Teteraphenylporphine in Dimethyl Sulfoxide". Inorg. Chem. 20 (11): 3763–3765. doi:10.1021/ic50225a038.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  9. G. C. Vogel and J. R. Stahlbush (1976). "Thermodynamic Study of the Adduct Formation of Zinc Tetraphenylporphine with Several Neutral Donors in Cyclohexane". Inorg. Chem. 16 (4): 950–953. doi:10.1021/ic50170a049.
  10. F. A. Walker, E. Hui, and J. M. Walker (1975) the Journal of The American Chemical Society, 87, 2375
  11. J. B. Kim, J. J. Leonard and F. R. Longo (1972). "A mechanistic study of the synthesis and spectral properties of meso-tetraphenylporphyrin". J. Am. Chem. Soc. 94 (11): 3986–3992. doi:10.1021/ja00766a056. PMID 5037983.
  12. Vinícius Claudio Zoldan, Ricardo Faccio and André Avelino Pasa (2015). "N and p type character of single molecule diodes". Scientific Reports. 5: 8350. Bibcode:2015NatSR...5E8350Z. doi:10.1038/srep08350. PMC 4322354. PMID 25666850.
  13. Karl-Heinz Pfoertner (2002) "Photochemistry" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a19_573
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