Singlet oxygen

Singlet oxygen

Names
IUPAC name Singlet oxygen
Systematic IUPAC name Dioxidene
Identifiers
3D model (JSmol)	Interactive image
ChEBI	CHEBI:26689
Gmelin Reference	491
InChI InChI=1S/O2/c1-2 Key: MYMOFIZGZYHOMD-UHFFFAOYSA-N
SMILES O=O
Properties
Chemical formula	O2
Molar mass	31.998 g·mol−1
Solubility in water	Reacts
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Singlet oxygen, systematically named dioxygen(singlet) and dioxidene, is a gaseous inorganic chemical with the formula O=O (also written as ¹
[O
_²] or ¹
O
_²), which is in a quantum state where all electrons are spin paired. It is kinetically unstable at ambient temperature, but the rate of decay is slow.

The lowest excited state of the diatomic oxygen molecule is a singlet state. It is a gas with physical properties differing only subtly from those of the more prevalent triplet ground state of O₂. In terms of its chemical reactivity, however, singlet oxygen is far more reactive toward organic compounds. It is responsible for the photodegradation of many materials but can be put to constructive use in preparative organic chemistry and photodynamic therapy. Trace amounts of singlet oxygen are found in the upper atmosphere and in polluted urban atmospheres where it contributes to the formation of lung-damaging nitrogen dioxide. ^{[1] : 355–68} It often appears and coexists confounded in environments that also generate ozone, such as pine forests with photodegradation of turpentine.^{[ citation needed ]}

The terms 'singlet oxygen' and 'triplet oxygen' derive from each form's number of electron spins. The singlet has only one possible arrangement of electron spins with a total quantum spin of 0, while the triplet has three possible arrangements of electron spins with a total quantum spin of 1, corresponding to three degenerate states.

In spectroscopic notation, the lowest singlet and triplet forms of O₂ are labeled ¹Δ_g and ³Σ⁻
_g, respectively. ^{[2] [3] [4]}

Electronic structure

Singlet oxygen refers to one of two singlet electronic excited states. The two singlet states are denoted ¹Σ⁺
_g and ¹Δ_g (the preceding superscript "1" indicates a singlet state). The singlet states of oxygen are 158 and 95 kilojoules per mole higher in energy than the triplet ground state of oxygen. Under most common laboratory conditions, the higher energy ¹Σ⁺
_g singlet state rapidly converts to the more stable, lower energy ¹Δ_g singlet state. ^[2] This more stable of the two excited states has its two valence electrons spin-paired in one π* orbital while the second π* orbital is empty. This state is referred to by the title term, singlet oxygen, commonly abbreviated ¹O₂, to distinguish it from the triplet ground state molecule, ³O₂. ^{[2] [3]}

Molecular orbital theory predicts the electronic ground state denoted by the molecular term symbol ³Σ^–
_g, and two low-lying excited singlet states with term symbols ¹Δ_g and ¹Σ⁺
_g. These three electronic states differ only in the spin and the occupancy of oxygen's two antibonding π_g-orbitals, which are degenerate (equal in energy). These two orbitals are classified as antibonding and are of higher energy. Following Hund's first rule, in the ground state, these electrons are unpaired and have like (same) spin. This open-shell triplet ground state of molecular oxygen differs from most stable diatomic molecules, which have singlet (¹Σ⁺
_g) ground states. ^[5]

Two less stable, higher energy excited states are readily accessible from this ground state, again in accordance with Hund's first rule; ^[6] the first moves one of the high energy unpaired ground state electrons from one degenerate orbital to the other, where it "flips" and pairs the other, and creates a new state, a singlet state referred to as the ¹Δ_g state (a term symbol, where the preceding superscripted "1" indicates it as a singlet state). ^{[2] [3]} Alternatively, both electrons can remain in their degenerate ground state orbitals, but the spin of one can "flip" so that it is now opposite to the second (i.e., it is still in a separate degenerate orbital, but no longer of like spin); this also creates a new state, a singlet state referred to as the ¹Σ⁺
_g state. ^{[2] [3]} The ground and first two singlet excited states of oxygen can be described by the simple scheme in the figure below. ^{[7] [8]}

Molecular orbital diagram of two singlet excited states as well as the triplet ground state of molecular dioxygen. From left to right, the diagrams are for: Δ_g singlet oxygen (first excited state), Σ
_g singlet oxygen (second excited state), and Σ
_g triplet oxygen (ground state). The lowest energy 1s molecular orbitals are uniformly filled in all three and are omitted for simplicity. The broad horizontal lines labelled π and π* each represent two molecular orbitals (for filling by up to 4 electrons in total). The three states only differ in the occupancy and spin states of electrons in the two degenerate π* antibonding orbitals.

The ¹Δ_g singlet state is 7882.4 cm⁻¹ above the triplet ³Σ⁻
_g ground state., ^{[3] [9]} which in other units corresponds to 94.29 kJ/mol or 0.9773 eV. The ¹Σ⁺
_g singlet is 13 120.9 cm^{−1 [3] [9]} (157.0 kJ/mol or 1.6268 eV) above the ground state.

Radiative transitions between the three low-lying electronic states of oxygen are formally forbidden as electric dipole processes. ^[10] The two singlet-triplet transitions are forbidden both because of the spin selection rule ΔS = 0 and because of the parity rule that g-g transitions are forbidden. ^[11] The singlet-singlet transition between the two excited states is spin-allowed but parity-forbidden.

The lower, O₂(¹Δ_g) state is commonly referred to as singlet oxygen. The energy difference of 94.3 kJ/mol between ground state and singlet oxygen corresponds to a forbidden singlet-triplet transition in the near-infrared at ~1270 nm. ^[12] As a consequence, singlet oxygen in the gas phase is relatively long lived (54-86 milliseconds), ^[13] although interaction with solvents reduces the lifetime to microseconds or even nanoseconds. ^[14] In 2021, the lifetime of airborne singlet oxygen at air/solid interfaces was measured to be 550 microseconds. ^[15]

The higher ¹Σ⁺
_g state is moderately short lived. In the gas phase, it relaxes primarily to the ground state triplet with a mean lifetime of 11.8 seconds. ^[10] However in solvents such as CS₂ and CCl₄, it relaxes to the lower singlet ¹Δ_g in milliseconds due to radiationless decay channels. ^[10]

Paramagnetism due to orbital angular momentum

Both singlet oxygen states have no unpaired electrons and therefore no net electron spin. The ¹Δ_g is however paramagnetic as shown by the observation of an electron paramagnetic resonance (EPR) spectrum. ^{[16] [17] [18]} The paramagnetism of the ¹Δ_g state is due to a net orbital (and not spin) electronic angular momentum. In a magnetic field the degeneracy of the ${\displaystyle M_{L}}$ levels is split into two levels with z projections of angular momenta +1ħ and −1ħ around the molecular axis. The magnetic transition between these levels gives rise to the ${\displaystyle g=1}$ EPR transition.

Production

Various methods for the production of singlet oxygen exist. Irradiation of oxygen gas in the presence of an organic dye as a sensitizer, such as rose bengal, methylene blue, or porphyrins—a photochemical method—results in its production. ^{[19] [9]} Large steady state concentrations of singlet oxygen are reported from the reaction of triplet excited state pyruvic acid with dissolved oxygen in water. ^[20] Singlet oxygen can also be produced by chemical procedures without irradiation. One chemical method involves the decomposition of triethylsilyl hydrotrioxide generated in situ from triethylsilane and ozone. ^[21]

(C₂H₅)₃SiH + O₃ → (C₂H₅)₃SiOOOH → (C₂H₅)₃SiOH + O₂(¹Δ_g)

Another method uses a reaction of hydrogen peroxide with sodium hypochlorite in aqueous solution: ^[19]

H₂O₂ + NaOCl → O₂(¹Δ_g) + NaCl + H₂O

A retro-Diels Alder reaction of the diphenylanthracene peroxide can also yield singlet oxygen, along with an diphenylanthracene: ^[22]

Retro-Diels Alder formation of singlet oxygen

A third method liberates singlet oxygen via phosphite ozonides, which are, in turn, generated in situ such as triphenyl phosphite ozonide. ^{[23] [24]} Phosphite ozonides will decompose to give singlet oxygen: ^[25]

(RO)₃P + O₃ → (RO)₃PO₃

(RO)₃PO₃ → (RO)₃PO + O₂(¹Δ_g)

An advantage of this method is that it is amenable to non-aqueous conditions. ^[25]

Reactions

Singlet oxygen-based oxidation of citronellol. This is a net, but not a true ene reaction. Abbreviations, step 1: H₂O₂, hydrogen peroxide; Na₂MoO₄ (catalyst), sodium molybdate. Step 2: Na₂SO₃ (reducing agent), sodium sulfite.

Because of differences in their electron shells, singlet and triplet oxygen differ in their chemical properties; singlet oxygen is highly reactive. ^[26] The lifetime of singlet oxygen depends on the medium and pressure. In normal organic solvents, the lifetime is only a few microseconds whereas in solvents lacking C-H bonds, the lifetime can be as long as seconds. ^{[25] [27]}

Unlike ground state oxygen, singlet oxygen participates in Diels–Alder [4+2]- and [2+2]-cycloaddition reactions and formal concerted ene reactions (Schenck ene reaction), causing photooxygenation. ^[25] It oxidizes thioethers to sulfoxides. Organometallic complexes are often degraded by singlet oxygen. ^{[28] [29]} With some substrates 1,2-dioxetanes are formed; cyclic dienes such as 1,3-cyclohexadiene form [4+2] cycloaddition adducts. ^[30]

The [4+2]-cycloaddition between singlet oxygen and furans is widely used in organic synthesis. ^{[31] [32]}

In singlet oxygen reactions with alkenic allyl groups, e.g., citronella, shown, by abstraction of the allylic proton, in an ene-like reaction, yielding the allyl hydroperoxide, R–O–OH (R = alkyl), which can then be reduced to the corresponding allylic alcohol. ^{[25] [33] [34] [35]}

In reactions with water, trioxidane, an unusual molecule with three consecutive linked oxygen atoms, is formed.^{[ citation needed ]}

Biochemistry

In photosynthesis, singlet oxygen can be produced from the light-harvesting chlorophyll molecules. One of the roles of carotenoids in photosynthetic systems is to prevent damage caused by produced singlet oxygen by either removing excess light energy from chlorophyll molecules or quenching the singlet oxygen molecules directly.

In mammalian biology, singlet oxygen is one of the reactive oxygen species, which is linked to oxidation of LDL cholesterol and resultant cardiovascular effects. Polyphenol antioxidants can scavenge and reduce concentrations of reactive oxygen species and may prevent such deleterious oxidative effects. ^[36]

Ingestion of pigments capable of producing singlet oxygen with activation by light can produce severe photosensitivity of skin (see phototoxicity, photosensitivity in humans, photodermatitis, phytophotodermatitis). This is especially a concern in herbivorous animals (see Photosensitivity in animals).

Singlet oxygen is the active species in photodynamic therapy.

Modified Jablonski diagram showing the mechanism of PDT

Analytical and physical chemistry

Red glow associated with decay of singlet oxygen to its triplet state.

Singlet oxygen luminesces concomitant with its decay to the triplet ground state. This phenomenon was first observed in the thermal degradation of the endo peroxide of rubrene. ^[38]

References

1. Wayne RP (1969). "Singlet Molecular Oxygen". In Pitts JN, Hammond GS, Noyes WA (eds.). Advances in Photochemistry. Vol. 7. pp. 311–71. doi:10.1002/9780470133378.ch4. ISBN   9780470133378.
2. Klán P, Wirz J (2009). Photochemistry of Organic Compounds: From Concepts to Practice (Repr. 2010 ed.). Chichester, West Sussex, U.K.: Wiley. ISBN   978-1405190886.
3. Atkins P, de Paula J (2006). Atkins' Physical Chemistry (8th ed.). W.H.Freeman. pp.  482–3. ISBN   978-0-7167-8759-4.
4. Hill C. "Molecular Term Symbols" (PDF). Archived from the original (PDF) on 5 September 2017. Retrieved 10 October 2016.
5. Levine IN (1991). Quantum Chemistry (4th ed.). Prentice-Hall. p. 383. ISBN   978-0-205-12770-2.
6. Frimer AA (1985). Singlet Oxygen: Volume I, Physical-Chemical Aspects. Boca Raton, Fla.: CRC Press. pp. 4–7. ISBN   9780849364396.
7. For triplet ground state on right side of diagram, see C.E.Housecroft and A.G.Sharpe Inorganic Chemistry, 2nd ed. (Pearson Prentice-Hall 2005), p.35 ISBN   0130-39913-2
8. For changes in singlet states on left and in centre, see F. Albert Cotton and Geoffrey Wilkinson. Advanced Inorganic Chemistry, 5th ed. (John Wiley 1988), p.452 ISBN   0-471-84997-9
9. Schweitzer C, Schmidt R (May 2003). "Physical Mechanisms of Generation and Deactivation of Singlet Oxygen". Chemical Reviews. 103 (5): 1685–757. doi:10.1021/cr010371d. PMID   12744692.
10. Weldon, Dean; Poulsen, Tina D.; Mikkelsen, Kurt V.; Ogilby, Peter R. (1999). "Singlet Sigma: The "Other" Singlet Oxygen in Solution". Photochemistry and Photobiology. 70 (4): 369–379. doi: 10.1111/j.1751-1097.1999.tb08238.x . S2CID   94065922.
11. Thomas Engel; Philip Reid (2006). Physical Chemistry. PEARSON Benjamin Cummings. p. 580. ISBN   978-0-8053-3842-3.
12. Guy P. Brasseur; Susan Solomon (January 15, 2006). Aeronomy of the Middle Atmosphere: Chemistry and Physics of the Stratosphere and Mesosphere. Springer Science & Business Media. pp. 220–. ISBN   978-1-4020-3824-2.
13. Physical Mechanisms of Generation and Deactivation of Singlet Oxygen Claude Schweitzer
14. Wilkinson F, Helman WP, Ross AB (1995). "Rate constants for the decay and reactions of the lowest electronically excited singlet state of molecular oxygen in solution. An expanded and revised compilation". J. Phys. Chem. Ref. Data . 24 (2): 663–677. Bibcode:1995JPCRD..24..663W. doi:10.1063/1.555965. S2CID   9214506.
15. Andrés M. Durantini (2021). "Interparticle Delivery and Detection of Volatile Singlet Oxygen at Air/Solid Interfaces". Environmental Science & Technology. 55 (6): 3559–3567. Bibcode:2021EnST...55.3559D. doi:10.1021/acs.est.0c07922. PMID   33660980. S2CID   232114444.
16. Hasegawa K, Yamada K, Sasase R, Miyazaki R, Kikuchi A, Yagi M (2008). "Direct measurements of absolute concentration and lifetime of singlet oxygen in the gas phase by electron paramagnetic resonance". Chemical Physics Letters. 457 (4): 312–314. Bibcode:2008CPL...457..312H. doi:10.1016/j.cplett.2008.04.031.
17. Ruzzi M, Sartori E, Moscatelli A, Khudyakov IV, Turro NJ (June 2013). "Time-resolved EPR study of singlet oxygen in the gas phase". The Journal of Physical Chemistry A. 117 (25): 5232–40. Bibcode:2013JPCA..117.5232R. CiteSeerX   10.1.1.652.974 . doi:10.1021/jp403648d. PMID   23768193.
18. Falick AM, et al. (1965). "Paramagnetic resonance spectrum of the ¹Δ_g oxygen molecule". J. Chem. Phys. 42 (5): 1837–1838. Bibcode:1965JChPh..42.1837F. doi:10.1063/1.1696199. S2CID   98040975.
19. Greer A (2006). "Christopher Spencer Foote's Discovery of the Role of Singlet Oxygen [¹O₂ (¹Δ_g)] in Photosensitized Oxidation Reactions". Acc. Chem. Res. 39 (11): 797–804. doi:10.1021/ar050191g. PMID   17115719.
20. Eugene AJ, Guzman MI (September 2019). "Production of Singlet Oxygen (¹O₂) during the Photochemistry of Aqueous Pyruvic Acid: The Effects of pH and Photon Flux under Steady-State O₂(aq) Concentration". Environmental Science and Technology. 53 (21): 12425–12432. Bibcode:2019EnST...5312425E. doi: 10.1021/acs.est.9b03742 . PMID   31550134.
21. Corey EJ, Mehrotra MM, Khan AU (April 1986). "Generation of ¹Δ_g from triethylsilane and ozone". Journal of the American Chemical Society. 108 (9): 2472–3. doi:10.1021/ja00269a070. PMID   22175617.
22. 裴, 坚 (2016). 基础有机化学[Basic Organic Chemistry] (4th ed.). 北京大学出版社. pp. 1072–1073. ISBN   978-7-301-27212-1.
23. Bartlett, Paul D.; Mendenhall, G. David; Durham, Dana L. (October 1980). "Controlled generation of singlet oxygen at low temperatures from triphenyl phosphite ozonide". The Journal of Organic Chemistry. 45 (22): 4269–4271. doi:10.1021/jo01310a001. ISSN   0022-3263.
24. Housecroft CE, Sharpe AG (2008). "Chapter 15: The group 16 elements". Inorganic Chemistry (3rd ed.). Pearson. p.  438 f. ISBN   9780131755536.
25. Wasserman HH, DeSimone RW, Chia KR, Banwell MG (2001). "Singlet Oxygen". Encyclopedia of Reagents for Organic Synthesis. e-EROS Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rs035. ISBN   978-0471936237.
26. Ho RY, Liebman JF, Valentine JS (1995). "Overview of the Energetics and Reactivity of Oxygen". In Foote CS (ed.). Active Oxygen in Chemistry. London: Blackie Academic & Professional. pp. 1–23. doi:10.1007/978-94-007-0874-7_1. ISBN   978-0-7514-0371-8.
27. Kuntner N (2018). "Modeling and simulation of electronic excitation in oxygen-helium discharges and plasma-assisted combustion". University of Stuttgart. doi = http://dx.doi.org/10.18419/opus-9925
28. Clennan EL, Pace A (2005). "Advances in singlet oxygen chemistry". Tetrahedron. 61 (28): 6665–6691. doi:10.1016/j.tet.2005.04.017.
29. Ogilby PR (August 2010). "Singlet oxygen: there is indeed something new under the sun". Chemical Society Reviews. 39 (8): 3181–209. doi:10.1039/b926014p. PMID   20571680.
30. Carey FA, Sundberg RJ (1985). Structure and mechanisms (2 ed.). New York: Plenum Press. ISBN   978-0306411984.
31. Montagnon, T.; Kalaitzakis, D.; Triantafyllakis, M.; Stratakis, M.; Vassilikogiannakis, G. (2014). "Furans and Singlet Oxygen - Why There Is More to Come from this Powerful Partnership". Chemical Communications. 50 (98): 15480–15498. doi:10.1039/C4CC02083A. PMID   25316254.
32. Ghogare, A.A.; Greer, A. (2016). "Using Singlet Oxygen to Synthesise Natural Products and Drugs". Chemical Reviews. 116 (17): 9994–10034. doi:10.1021/acs.chemrev.5b00726. PMID   27128098.
33. Stephenson LM, Grdina MJ, Orfanopoulos M (November 1980). "Mechanism of the ene reaction between singlet oxygen and olefins". Accounts of Chemical Research. 13 (11): 419–425. doi:10.1021/ar50155a006.
34. This reaction is not a true ene reaction, because it is not concerted; singlet oxygen forms an "epoxide oxide" exciplex, which then abstracts the hydrogen. See Alberti et al, op. cit.
35. Alsters PL, Jary W, Nardello-Rataj V, Jean-Marie A (2009). "Dark Singlet Oxygenation of β-Citronellol: A Key Step in the Manufacture of Rose Oxide". Organic Process Research & Development . 14: 259–262. doi:10.1021/op900076g.
36. Karp G, van der Geer P (2004). Cell and molecular biology: concepts and experiments (4th ed., Wiley International ed.). New York: J. Wiley & Sons. p. 223. ISBN   978-0471656654.
37. Devika, Sivakumar; Rakhi, Raju; Y.T., Kamal; Shahana, Salam (3 January 2023). Porphyrinoid Photosensitizers for Targeted and Precise Photodynamic Therapy: Progress in Fabrication. London: intechopen. p. 145-174. ISBN   978-1-83768-471-7.
38. Franz, Karl A.; Kehr, Wolfgang G.; Siggel, Alfred; Wieczoreck, Jürgen; Adam, Waldemar (2000). "Luminescent Materials". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a15_519. ISBN   3-527-30673-0.

Further reading

• Mulliken RS (1928). "Interpretation of the atmospheric oxygen bands; electronic levels of the oxygen molecule". Nature . 122 (3075): 505. Bibcode:1928Natur.122..505M. doi: 10.1038/122505a0 . S2CID   4105859.
• Chou, Pi-Tai; Wei, Guor-Tzo; Lin, Chih-Hung; Wei, Ching-Yen; Chang, Chie-Hung (1996-01-01). "Direct Spectroscopic Evidence of Photosensitized O2 765 nm (1Σ+g → 3Σ-g) and O2 Dimol 634 and 703 nm ((1Δg)2 → (3Σ-g)2) Vibronic Emission in Solution". Journal of the American Chemical Society. 118 (12): 3031–3032. doi:10.1021/ja952352p. ISSN   0002-7863.
• Földes T, Čermák P, Macko M, Veis P, Macko P (January 2009). "Cavity ring-down spectroscopy of singlet oxygen generated in microwave plasma". Chemical Physics Letters. 467 (4–6): 233–236. Bibcode:2009CPL...467..233F. CiteSeerX   10.1.1.186.9272 . doi:10.1016/j.cplett.2008.11.040.
• Nosaka Y, Daimon T, Nosaka, AY, Murakami Y (2004). "Singlet oxygen formation in photocatalytic TiO₂ aqueous suspension". Phys. Chem. Chem. Phys. 6 (11): 2917–2918. Bibcode:2004PCCP....6.2917N. doi:10.1039/B405084C.</ref>

• Bodner, G.M. (2002) Lecture Demonstration Movie Sheets: 8.4 Liquid Oxygen—Paramagnetism and Color, West Lafayette, IN, USA: Purdue University Department of Chemistry, see Liquid Oxygen---Paramagnetism and Color and Lecture Demonstration Movie Sheets, accessed 11 August 2015; alternatively, see Bodner, G.M.; K. Keyes & T.J. Greenbowe (1995) Purdue University Lecture Demonstration Manual, 2nd Edn, p. TBD, New York, NY, USA: John Wiley and Sons. [Earlier appearing reference on magnetic properties of oxygen states.]

External links

• The NIST webbook on oxygen
• Photochemistry & Photobiology tutorial on Singlet Oxygen
• Demonstration of the Red Singlet Oxygen Dimol Emission (Purdue University)