Triplet states and radicals

Triplet state and Z/E isomerization of p-styrylstilbene induced by various sensitizers and the T, potential energy curves and one way photoisomerization (c -> t only) of styryl aromatics " are the subject of two papers on the behaviour of triplets of this class of compound. Time resolved resonance Raman spectra of the triplet state and radical cation of 5-dibenzosuberenol has been used to study and examine the mechanism of photoisomerization of this compound. ... 

This review is divided into the following sections. First, EPR measurements of g-tensors of flavoproteins and the modulation of the principal values of g by the protein surroundings of the cofactor are discussed. Then, two recent examples of application of pulsed ENDOR spectroscopy will be reviewed, and, finally, time-resolved EPR spectroscopy, that is most favorably used to study photo-excited triplet states and radical pairs, will be introduced. 

Both CSs and CSs were also successfully generated by the fragmentation of ionized 4,5-dioxo-2-thioxo-l,3-dithione (65) and 2-thioxo-l,3-dithiole (66) (90JA3750). Tire three sulfur atoms in the anion and cation radicals were chemically equivalent, suggesting that they take the D h (or C2u) form (67 or 68). On the other hand, under similar conditions, 3-thioxo-1,2-dithiole (69) yielded two isomeric cation radicals the (or 2 ) form and the carbon disulfide 5-sulfide form (70). Ab initio calculations on three electronic states of CS3 at the 6-31G -l-ZPVE level indicated that the C21, form (68) was more stable than the carbon disulfide 5-sulfide form (70) in the neutral (both singlet and triplet states) and the anion radical states, but 68 was less stable than 70 in the radical cation state. 

Copper corrole is a diamagnetic copper(III) complex which at higher temperatures exists in the triplet state and is then best formulated as a copper(II) corrole-n-radical. 

Lu, C. Y. Lui, Y.Y. (2002). Electron transfer oxidation of tryptophan and tyrosine by triplet states and oxidized radicals of flavin sensitizers a laser flash photolysis study. Biochimica et Biophysica Acta (BBA) - General Subjects, Vol. 1571, No.l, (May 2002), pp. 71-76, ISSN 0304-4165... 

So far, the solid state type I reaction has been reliable only when followed by the irreversible loss of CO to yield alkyl-alkyl radical species (RP-B or BR-B) in a net de-carbonylation process. The type 11 reaction relies on the presence of a y-hydrogen that can be transferred to the carbonyl oxygen to generate the 1,4-hydroxy-biradical (BR C). The type-1 and type-11 reactions are generally favored in the excited triplet state and they often compete with each other and with other excited state decay pathways. While the radical species generated in these reactions generate complex product mixtures in solution, they tend to be highly selective in the crystalline state. 

On the other hand, oxidation of a DNA base by a triplet state of the an-thraquinone (AQ5"3) generates a contact ion pair in an overall triplet state, and back electron transfer from this species to form ground states is prohibited by spin conservation rules. Consequently, the lifetime of the triplet radical ion pair is long enough to permit the bimolecular reaction of AQ- with 02 to form superoxide (02 ) and regenerate the anthraquinone. 

At this point let us briefly consider the relationship between the carbonyl triplet state and another system capable of hydrogen atom abstraction alkoxy radicals. A comparison of the differences and/or similarities between the reactivity of the carbonyl triplet and that of an alkoxy radical should indicate whether the triplet state behaves as a normal ground state radical or if electronic excitation imparts unique properties leading to reactions not characteristic of ground state radicals. 

A general theory of the aromatic hydrocarbon radical cation and anion annihilation reactions has been forwarded by G. J. Hoytink 210> which in particular deals with a resonance or a non-resonance electron transfer mechanism leading to excited singlet or triplet states. The radical ion chemiluminescence reactions of naphthalene, anthracene, and tetracene are used as examples. 

For a more in-depth interpretation of the inertness of dioxygen, the fact that 02 is a triplet state bi-radical, i.e. it has two unpaired electrons in the 2jig orbitals, needs to be considered. It follows that the oxidation of singlet state substrates by the triplet 02 to form singlet products is spin-forbidden and, as a consequence, relatively slow. 

The triplet reaction of 2-nitrodibenzo[fc,primary amines (n-propylamine and benzylamine) was studied110 in polar and apolar solvents. In polar solvents, the irradiation results in the formation of two isomeric compounds, (alky-lamino)hydroxynitrodiphenyl ether andiV-(alkylamino)-2-nitrophenoxazine (equation 54). In apolar solvents, only the nitrophenoxazine is obtained. In polar solvents, the exciplex formed between the 2-n i trodi benzol h,e [ 1,4]dioxin triplet state and amines dissociates to the solvated radical ions, from which the diphenyl ether arises. 1-Nitrodibenzo[fr,e][l,4]dioxin is stable even on prolonged irradiation. 

The absorption band around 520 nm is very similar to that of polystyrene excimer (2,3,5). The decay follows first order kinetics with a lifetime of 20 ns. The decay rate agrees with that of the excimer fluorescence and excimer absorption. The longer life absorptions, attributed to the triplet states and free radicals (2,5), were observed at wave lengths <400 nm, although the anionic species of polystyrene with the absorption maximum at 410 nm as seen in solid films (cf. Figure 5) was not observed. Figure 9 shows the absorption spectrum observed in the pulse radiolysis of CMS solution in cyclohexane. 

The photooxidation of p-phenylenediamine to the Wurster s Blue radical cation apparently proceeds by photoionization of the excited triplet state of the neutral molecule,219 and it has been suggested that the delayed fluorescence of perylene may be partly due to photoionization of its triplet state and slow subsequent recombination of... 

Nitric oxide is the simplest stable molecule with an odd number of electrons. Because of its unpaired electron, it is paramagnetic at room temperature (the lowest lying energy level, X2U/z, is diamagnetic), ionizes relatively easily, and is highly reactive with other paramagnetic species, such as NOz and Oa. It is an efficient scavenger of free radicals and triplet states and has been used frequently for this purpose in photochemical and thermal studies. 

Luminescence is seldom observed from free radicals and radical ions because of the low energy of the lowest excited states of open-shell species, the benzophenone ketyl radical being however a noteworthy exception. There are few reports of actual photochemical reactions of free radicals, but the situation is different with biradicals such as carbenes. These have two unpaired electrons and can exist in singlet or triplet states and they take part in addition and insertion reactions (Figure 4.90). 

It is known that for phenyl alkyl ketones both the Type I and Type II reactions occur only from triplet state. The radical pair formed from a-cleavage undergo disproportionation resulting in Type I products or recombine to regenerate the ground state ketone. The latter process reduces the efficiency of Type I product formation. 

Adam W, Arnold MA, Grune M, Nau WM, Pischel U, Saha-Moller CR (2002b) Spiroimiodihydantoin is the major product in the photooxidation of 2 -deoxyguanosine by triplet states and oxyl radicals generated from hydroxyacetophenone photolysis and dioxetane thermolysis. Org Lett 4 537-540... 

The mechanism of this reaction shows that excitation of the substrate gave an n,n triplet state, but this excited state was unable to dissociate the carbon-iodine bond. This was demonstrated by showing that the n,n triplet state, when sensitized by chrysene, did not produce coupling products. Probably, the reaction occurred in an excited a,a triplet state mainly localized on the carbon-iodine bond, and the interaction between this triplet state and aromatic compounds led to homolytic cleavage of the C-I bond with the formation of both a 5-thienyl radical and a complex between the aromatic compound and the halogen atom. The formation of this complex was demonstrated by the presence of a short-lived transient with Amax = 510 nm, showing a second-order decay kinetics and a half-life of ca. 0.4 (is in laser flash photolysis. The thienyl radical thus formed... 

Electron spin resonance (ESR) spectroscopy is of application to organic species containing unpaired electrons radicals, radical ions and triplet states, and is much more sensitive than NMR it is an extremely powerful tool in the field of radical chemistry (see Chapter 10). Highly unstable radicals can be generated in situ or, if necessary, trapped into solid matrices at very low temperatures. Examples of the application of this techniques include study of the formation of radical cations of methoxylated benzenes by reaction with different strong oxidants in aqueous solution [45], and the study of the photodissociation of N-trityl-anilines [46],... 

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