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| verifiedrevid = 311593626 |
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| verifiedrevid = 413892535 |
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| Name = Tetraphenylporphyrin |
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| Name = Tetraphenylporphyrin |
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| ImageFile1 = H2TPP.png|Lewis structure for meso-tetraphenylporphyrin |
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| ImageSize1 = 150px |
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| ImageName = Tetraphenylporphyrin |
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| ImageName = Tetraphenylporphyrin |
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| OtherNames = 5,10,15,20-Tetraphenylporphin, H2TPP |
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| ImageFile1 = H2TPP.png |
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| ImageSize1 = 150px |
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| ImageAlt1 = Lewis structure for meso-tetraphenylporphyrin |
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| ImageFile2 = Tetraphenylporphyrin-3D-balls.png |
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| ImageAlt2 = Ball-and-stick model of the tetraphenylporphyrin molecule |
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| IUPACName = 5,10,15,20-Tetraphenyl-21''H'',23''H''-porphyrin |
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| SystematicName = -2,4,6,8-Tetraphenyl-1<sup>1</sup>''H'',5<sup>1</sup>''H''-1,3,5,7(2,5)-tetrapyrrolacyclooctaphane-1<sup>2</sup>(2),1<sup>5</sup>(8),3<sup>5</sup>(4),6(7<sup>2</sup>)-tetraene |
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| OtherNames = 5,10,15,20-Tetraphenylporphin, TPP, H2TPP |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 917-23-7 |
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| CASNo = 917-23-7 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = SDB2SH8G5K |
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| Beilstein = 379542 |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL = 436524 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 52279 |
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| MeSHName = C509964 |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| ChemSpiderID = 10291672 |
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| PubChem = 86280046 |
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| SMILES = 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 |
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| 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- |
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| InChIKey = YNHJECZULSZAQK-LWQDQPMZBQ |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 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- |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = YNHJECZULSZAQK-LWQDQPMZSA-N |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Density = 1.27 g/cm<sup>3</sup> |
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| Density = 1.27 g/cm<sup>3</sup> |
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| Solubility = insoluble in water |
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| Solubility = insoluble in water |
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| MeltingPt = |
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| MeltingPtC = |
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| BoilingPt = |
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| BoilingPtC = |
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| Section3 = {{Chembox Hazards |
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| Section3 = {{Chembox Hazards |
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| GHSPictograms = {{GHS07}} |
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| RPhrases = |
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| GHSSignalWord = Warning |
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| HPhrases = {{H-phrases|302|312|332}} |
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| PPhrases = {{P-phrases|261|264|270|271|280|301+312|302+352|304+312|304+340|312|322|330|363|501}} |
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'''Tetraphenylporphyrin''', abbreviated H<sub>2</sub>TPP, is a synthetic ] that resembles naturally occurring ]s. Porphyrins are dyes and cofactors found in ] and ]s and are related to ] and ]. The study of naturally-occurring porphyrins is complicated by their low symmetry and the presence of polar substituents. Tetraphenylporphyrin is ], symmetrically substituted, and easily synthesized. The compound is a dark purple solid that dissolves in nonpolar organic solvents such as ] and ]. |
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'''Tetraphenylporphyrin''', abbreviated TPP or H<sub>2</sub>TPP, is a synthetic ] that resembles naturally occurring ]s. Porphyrins are dyes and cofactors found in ] and ]s and are related to ] and ]. The study of naturally occurring porphyrins is complicated by their low symmetry and the presence of polar substituents. Tetraphenylporphyrin is ], symmetrically substituted, and easily synthesized. The compound is a dark purple solid that dissolves in nonpolar organic solvents such as ] and ]. |
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==Synthesis and structure== |
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==Synthesis and structure== |
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Tetraphenylporphyrin is prepared by the reaction of ] and ] in refluxing ], the so-called Rothemund method:<ref>{{cite journal | author = A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour and L. Korsakoff | title = A simplified synthesis for meso-tetraphenylporphine | year = 1967 | journal = ] | volume = 32 | issue = 2 | pages = 476–476 | doi = 10.1021/jo01288a053 }}</ref> |
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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.<ref>{{cite journal | author = P. Rothemund | title = A New Porphyrin Synthesis. The Synthesis of Porphin | year = 1936 | journal = ] | volume = 58 | issue = 4 | pages = 625–627 | doi = 10.1021/ja01295a027 }}</ref> 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:<ref>{{cite journal | author = A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour and L. Korsakoff | title = A simplified synthesis for meso-tetraphenylporphine | year = 1967 | journal = ] | volume = 32 | issue = 2 | pages = 476 | doi = 10.1021/jo01288a053 }}</ref> |
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:8 C<sub>4</sub>H<sub>4</sub>NH + 8 C<sub>6</sub>H<sub>5</sub>CHO + 3 O<sub>2</sub> → 2 (C<sub>6</sub>H<sub>5</sub>C)<sub>4</sub>(C<sub>4</sub>H<sub>2</sub>N)<sub>2</sub>(C<sub>4</sub>H<sub>2</sub>NH)<sub>2</sub> + 14 H<sub>2</sub>O |
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:8 C<sub>4</sub>H<sub>4</sub>NH + 8 C<sub>6</sub>H<sub>5</sub>CHO + 3 O<sub>2</sub> → 2 (C<sub>6</sub>H<sub>5</sub>C)<sub>4</sub>(C<sub>4</sub>H<sub>2</sub>N)<sub>2</sub>(C<sub>4</sub>H<sub>2</sub>NH)<sub>2</sub> + 14 H<sub>2</sub>O |
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Despite low yields, the synthesis of H<sub>2</sub>TPP is a common experiment in university teaching labs.<ref>{{cite journal | title = Microscale Synthesis and <sup>1</sup>H NMR Analysis of Tetraphenylporphyrins | author = Falvo, RaeAnne E.; Mink, Larry M.; Marsh, Diane F. | journal = J. Chem. Educ. | volume = 1999 | issue = 76 | pages = 237}}</ref><ref>Girolami, G. S.; Rauchfuss, T. B.; Angelici, R. J., Synthesis and Technique in Inorganic Chemistry, University Science Books: Mill Valley, CA, 1999.ISBN 0935702482</ref> |
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Despite its modest yields, the synthesis of H<sub>2</sub>TPP is a common experiment in university teaching labs.<ref>{{cite journal | title = Microscale Synthesis and <sup>1</sup>H NMR Analysis of Tetraphenylporphyrins |author1=Falvo, RaeAnne E. |author2=Mink, Larry M. |author3=Marsh, Diane F. | journal = J. Chem. Educ. | volume = 1999 | issue = 76 | pages = 237 | doi=10.1021/ed076p237| year = 1999 |bibcode=1999JChEd..76..237M }}</ref><ref>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}}</ref> Highly efficient routes to H<sub>2</sub>TPP and many analogues involve the air-free condensation of the pyrrole and aldehyde to give the ]. In this so-called Lindsey synthesis of meso-substituted porphyrins, the porphyrinogen is subsequently oxidized to deliver the porphyrin.<ref>{{cite encyclopedia|editor1= Kadish, Karl M. |editor2=Smith, Kevin M. |editor3=Guilard, Roger|title=Synthesis of meso-substituted porphyrins|author= Lindsey, Jonathan S.|encyclopedia=Porphyrin Handbook|year=2000|volume=1|pages=45–118|isbn=0-12-393200-9}}</ref> |
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The porphyrin belongs to the ] C<sub>2h</sub>, the low symmetry being due to the orientation of the two N-H bonds, which project out of the plane of the four pyrrole rings. Unlike natural porphyrins, H<sub>2</sub>TPP is substituted at the oxidatively sensitive "meso" carbon positions, and hence the compound is sometimes called ''meso''-tetraphenylporphyrin. Another synthetic porphyrin, octaethylporphyrin (H<sub>2</sub>OEP) does have a substitution pattern that is biomimetic. Many derivatives of tetraphenylporphyrin are known, including those prepared from substituted benzaldehydes. One of the first functional analogues of ] was the ferrous derivative of the "Picket-Fence Porphyrin," which is structurally related to H<sub>2</sub>TPP, being derived via the condenation 2-nitrobenzaldehyde and pyrrole. H<sub>2</sub>TPP can be ] to give water-soluble derivatives, e.g. ]: |
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The conjugate base of the porphyrin, TPP<sup>2−</sup>, belongs to the ] D<sub>4h</sub> while its hydrogenated counterpart H<sub>2</sub>(TPP) is D<sub>2h</sub>.{{Cn|date=February 2022}} Unlike natural porphyrins, H<sub>2</sub>TPP is substituted at the oxidatively sensitive "meso" carbon positions, and hence the compound is sometimes called ''meso''-tetraphenylporphyrin. Another synthetic porphyrin, ] (H<sub>2</sub>OEP) 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 ] 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. |
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<gallery caption="Metal-TPP Complexes" widths="160px" heights="100px" > |
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File:PicketFenceGenericRevised.png|A picket-fence porphyrin complex of Fe, with axial coordination sites occupied by methylimidazole (green) and ] (R = amide groups).<ref>S. J. Lippard, J. M. Berg “Principles of Bioinorganic Chemistry” University Science Books: Mill Valley, CA; 1994. {{ISBN|0-935702-73-3}}.</ref> |
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File:FeTPP(CCl2)Mansuy.png|Structure of Fe(TPP)CC(C<sub>6</sub>H<sub>4</sub>Cl)<sub>2</sub>, one of several iron carbenoid complexes reported by ].<ref>{{cite journal|doi=10.1021/ic00279a023|title=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)|journal=Inorganic Chemistry|volume=27|issue=6|pages=1052–1056|year=1988|last1=Mansuy|first1=Daniel|last2=Battioni|first2=Jean Paul|last3=Lavallee|first3=David K.|last4=Fischer|first4=Jean|last5=Weiss|first5=Raymond}}</ref> |
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</gallery> |
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] derivatives of TPP are also well known to give water-soluble derivatives, e.g. ]: |
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:4 SO<sub>3</sub> + (C<sub>6</sub>H<sub>5</sub>C)<sub>4</sub>(C<sub>4</sub>H<sub>2</sub>N)<sub>2</sub>(C<sub>4</sub>H<sub>2</sub>NH)<sub>2</sub> |
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:4 SO<sub>3</sub> + (C<sub>6</sub>H<sub>5</sub>C)<sub>4</sub>(C<sub>4</sub>H<sub>2</sub>N)<sub>2</sub>(C<sub>4</sub>H<sub>2</sub>NH)<sub>2</sub> |
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→ (HO<sub>3</sub>SC<sub>6</sub>H<sub>4</sub>C)<sub>4</sub>(C<sub>4</sub>H<sub>2</sub>N)<sub>2</sub>(C<sub>4</sub>H<sub>2</sub>NH)<sub>2</sub> + 4 H<sub>2</sub>O |
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→ (HO<sub>3</sub>SC<sub>6</sub>H<sub>4</sub>C)<sub>4</sub>(C<sub>4</sub>H<sub>2</sub>N)<sub>2</sub>(C<sub>4</sub>H<sub>2</sub>NH)<sub>2</sub> + 4 H<sub>2</sub>O |
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==Complexes== |
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==Complexes== |
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{{main|Transition metal porphyrin complexes}} |
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Complexation can be thought of as proceeding via the conversion of H<sub>2</sub>TPP to TPP<sup>2-</sup>, with 4-fold symmetry. The metal insertion process proceeds via several step, not via the dianion. The resulting complexes are symmetrical with simple ] or ]. For example, Cu(TPP) has D<sub>4h</sub> symmetry. The corresponding iron complexes are more complex owing to variable oxidation states and coordination numbers. Well-studied derivatives include the ferric compounds, e.g. Fe(TPP)Cl and the ] <sub>2</sub>O, and ferrous compounds, e.g. Fe(TPP)CO(L) (L = imidazole, pyridine). |
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Complexation can be thought of as proceeding via the conversion of H<sub>2</sub>TPP to TPP<sup>2−</sup>, with 4-fold symmetry. The metal insertion process proceeds via several steps, not via the dianion. Representative complexes: |
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*Cu(TPP)<ref>{{cite journal | author = R. F. Pasternack, G. C. Vogel, C. A. Skowronek, R. K. Harries and J. G. Miller| title = Copper(II) Incorporation into Teteraphenylporphine in Dimethyl Sulfoxide| year = 1981 | journal = Inorg. Chem. | volume = 20 | issue = 11 | pages = 3763–3765 | doi = 10.1021/ic50225a038}}</ref> |
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*Zn(TPP)L<sub>x</sub><ref name=vogel1976>{{cite journal | author = G. C. Vogel and J. R. Stahlbush| title = Thermodynamic Study of the Adduct Formation of Zinc Tetraphenylporphine with Several Neutral Donors in Cyclohexane| year = 1976 | journal = Inorg. Chem. | volume = 16 | issue = 4 | pages = 950–953 | doi = 10.1021/ic50170a049}}</ref> |
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*VO(TPP)<ref>F. A. Walker, E. Hui, and J. M. Walker (1975) the Journal of The American Chemical Society, 87, 2375</ref> |
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*] |
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==Optical properties== |
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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%.<ref>{{cite journal | author = J. B. Kim, J. J. Leonard and F. R. Longo | title = A mechanistic study of the synthesis and spectral properties of meso-tetraphenylporphyrin. | year = 1972 | journal = ] | volume = 94 | issue = 11 | pages = 3986–3992 | doi = 10.1021/ja00766a056 | pmid = 5037983 }}</ref> |
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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.<ref name=vogel1976/> |
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==Applications== |
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==Applications== |
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] (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, H<sub>2</sub>TPP and TPP molecules. While scanning image (d), excess voltage was applied to H<sub>2</sub>TPP at the black dot, which instantly removed hydrogen, as shown in the bottom part of (d) and in the re-scan image (e).<ref name=r1/>]] |
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H<sub>2</sub>TPP is a ] for the production of ].<ref>Karl-Heinz Pfoertner "Photochemistry" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. {{DOI|10.1002/14356007.a19_573}}</ref> |
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H<sub>2</sub>TPP is a ] for the production of ].<ref>Karl-Heinz Pfoertner (2002) "Photochemistry" in ''Ullmann's Encyclopedia of Industrial Chemistry'', Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a19_573}}</ref> Its molecules have potential applications in ], as they show diode-like behavior that can be altered for each individual molecule.<ref name=r1>{{cite journal|doi=10.1038/srep08350|pmid=25666850|pmc=4322354|title=N and p type character of single molecule diodes|journal=Scientific Reports|volume=5|pages=8350|year=2015|author=Vinícius Claudio Zoldan, Ricardo Faccio and André Avelino Pasa|bibcode= }}</ref> |
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==References== |
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==References== |
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{{Reflist}} |
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