Singlet oxygen - Misplaced Pages

(Redirected from Dioxygen molecule) Oxygen with all of its electrons spin paired

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/c1-2Key: MYMOFIZGZYHOMD-UHFFFAOYSA-N
SMILES O=O
Properties
Chemical formula	O₂
Molar mass	31.998 g·mol
Solubility in water	Reacts
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Infobox references

Chemical compound

Singlet oxygen, systematically named dioxygen(singlet) and dioxidene, is a gaseous inorganic chemical with the formula O=O (also written as
or
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. It often appears and coexists confounded in environments that also generate ozone, such as pine forests with photodegradation of turpentine.

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 Δ_g and Σ
_g, respectively.

Electronic structure

Singlet oxygen refers to one of two singlet electronic excited states. The two singlet states are denoted Σ
_g and Δ_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 Σ
_g singlet state rapidly converts to the more stable, lower energy Δ_g singlet state. 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 O₂, to distinguish it from the triplet ground state molecule, O₂.

Molecular orbital theory predicts the electronic ground state denoted by the molecular term symbol Σ
_g, and two low-lying excited singlet states with term symbols Δ_g and Σ
_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 (Σ
_g) ground states.

Two less stable, higher energy excited states are readily accessible from this ground state, again in accordance with Hund's first rule; 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 Δ_g state (a term symbol, where the preceding superscripted "1" indicates it as a singlet state). 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 Σ
_g state. The ground and first two singlet excited states of oxygen can be described by the simple scheme in the figure below.

The Δ_g singlet state is 7882.4 cm above the triplet Σ
_g ground state., which in other units corresponds to 94.29 kJ/mol or 0.9773 eV. The Σ
_g singlet is 13 120.9 cm (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. 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. The singlet-singlet transition between the two excited states is spin-allowed but parity-forbidden.

The lower, O₂(Δ_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. As a consequence, singlet oxygen in the gas phase is relatively long lived (54-86 milliseconds), although interaction with solvents reduces the lifetime to microseconds or even nanoseconds. In 2021, the lifetime of airborne singlet oxygen at air/solid interfaces was measured to be 550 microseconds.

The higher Σ
_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. However in solvents such as CS₂ and CCl₄, it relaxes to the lower singlet Δ_g in milliseconds due to radiationless decay channels.

Paramagnetism due to orbital angular momentum

Both singlet oxygen states have no unpaired electrons and therefore no net electron spin. The Δ_g is however paramagnetic as shown by the observation of an electron paramagnetic resonance (EPR) spectrum. The paramagnetism of the Δ_g state is due to a net orbital (and not spin) electronic angular momentum. In a magnetic field the degeneracy of the $M_{L}$ 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 $g=1$ 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. Large steady state concentrations of singlet oxygen are reported from the reaction of triplet excited state pyruvic acid with dissolved oxygen in water. 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.

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

Another method uses a reaction of hydrogen peroxide with sodium hypochlorite in aqueous solution:

H₂O₂ + NaOCl → O₂(Δ_g) + NaCl + H₂O

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

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. Phosphite ozonides will decompose to give singlet oxygen:

(RO)₃P + O₃ → (RO)₃PO₃

(RO)₃PO₃ → (RO)₃PO + O₂(Δ_g)

An advantage of this method is that it is amenable to non-aqueous conditions.

Reactions

Because of differences in their electron shells, singlet and triplet oxygen differ in their chemical properties; singlet oxygen is highly reactive. 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.

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

The -cycloaddition between singlet oxygen and furans is widely used in organic synthesis.

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.

In reactions with water, trioxidane, an unusual molecule with three consecutive linked oxygen atoms, is formed.

Biochemistry

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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.

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.

Analytical and physical chemistry

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.

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