Anthracene reaction + singlet

Methyl-4,5-diphenyloxazole in methanol containing methylene blue as sensitizer irradiated 6 hrs. with a 150 w. floodlamp N-acetyldibenzamide. Y 86%. Also from the isomeric 4-methyl-2,5-diphenyloxazole and f. e. s. H. H. Wasser-man and M. B. Floyd, Tetrahedron SuppL 7, 441 (1966) with 9,10-diphenyl-anthracene peroxide, singlet oxygen reactions, s. Am. Soc. 89, 3073 (1967). 

The single-electron transfer from one excited component to the other component acceptor, as the critical step prior to cycloaddition of photo-induced Diels Alder reactions, has been demonstrated [43] for the reaction of anthracene with maleic anhydride and various maleimides carried out in chloroform under irradiation by a medium-pressure mercury lamp (500 W). The (singlet) excited anthracene ( AN ), generated by the actinic light, is quenched by dienophile... 

We have already discussed one of the earliest photoreactions to be studied, that is, the (4w + 4w) photodimerization of anthracene. That the singlet state was involved in this reaction was conclusively shown in the period 1955-1957. The first reaction in which the triplet state of the molecule was shown to be involved was the photoreduction of benzophenone by Hammond and co-workersa) and Backstrom and co-workers<2) 1959-1961. This was the first in a series of many papers from Hammond s laboratory... 

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. 

Photosensitization of diaryliodonium salts by anthracene occurs by a photoredox reaction in which an electron is transferred from an excited singlet or triplet state of the anthracene to the diaryliodonium initiator.13"15,17 The lifetimes of the anthracene singlet and triplet states are on the order of nanoseconds and microseconds respectively, and the bimolecular electron transfer reactions between the anthracene and the initiator are limited by the rate of diffusion of reactants, which in turn depends upon the system viscosity. In this contribution, we have studied the effects of viscosity on the rate of the photosensitization reaction of diaryliodonium salts by anthracene. Using steady-state fluorescence spectroscopy, we have characterized the photosensitization rate in propanol/glycerol solutions of varying viscosities. The results were analyzed using numerical solutions of the photophysical kinetic equations in conjunction with the mathematical relationships provided by the Smoluchowski16 theory for the rate constants of the diffusion-controlled bimolecular reactions. 

Figure 4. Electronic energy level diagram for anthracene illustrating the photophysical transitions (including reaction with the initiator from both the singlet and triplet states) and the associated kinetic constants.

Here A, lA, and3A represent anthracene in the ground state, the first excited singlet state and first excited triplet state, respectively. In addition, I represents the onium salt initiation, while Rs and Rt correspond to the reactive centers formed by reaction of the onium salt with the excited singlet and triplet state anthracene, respectively. 

The main features of the chemiluminescence mechanism are exemplarily illustrated in Scheme 11 for the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of imidazole (IMI-H) as base catalyst and the chemiluminescent activators (ACT) anthracene, 9,10-diphenylanthracene, 2,5-diphenyloxazole, perylene and rubrene. In this mechanism, the replacement of the phenolic substituents in TCPO by IMI-H constitutes the slow step, whereas the nucleophilic attack of hydrogen peroxide on the intermediary l,l -oxalyl diimidazole (ODI) is fast. This rate difference is manifested by a two-exponential behavior of the chemiluminescence kinetics. The observed dependence of the chemiexcitation yield on the electrochemical characteristics of the activator has been rationalized in terms of the intermolecular CIEEL mechanism (Scheme 12), in which the free-energy balance for the electron back-transfer (BET) determines whether the singlet-excited activator, the species responsible for the light emission, is formed ... 

The peroxyoxalate system is the only intermolecular chemiluminescent reaction presumably involving the (71EEL sequence (Scheme 44), which shows high singlet excitation yields (4>s), as confirmed independently by several authors Moreover, Stevani and coworkers reported a correlation between the singlet quantum yields, extrapolated to infinite activator concentrations (4> ), and the free energy involved in back electron-transfer (AG bet), as well as between the catalytic electron-transfer/deactivation rate constants ratio, ln( cAx( i3), and E j2° (see Section V). A linear correlation of ln( cAx( i3) and E /2° was obtained for the peroxyoxalate reaction with TCPO and H2O2 catalyzed by imidazole and for the imidazole-catalyzed reaction of 57, both in the presence of five activators commonly used in CIEEL studies (anthracene, DPA, PPO, perylene and rubrene). A further confirmation of the validity of the CIEEL mechanism in the excitation step of... 

In 1963, E. J. Bowen published his classic review The Photochemistry of Aromatic Hydrocarbon Solutions, in which he described two major reaction pathways for PAHs irradiated in organic solvents photodimerization and photooxidation mediated by the addition of singlet molecular oxygen, 02 ) (or simply 102), to a PAH (e.g., anthracene). For details on the spectroscopy and photochemistry of this lowest electronically excited singlet state of molecular oxygen, see Chapter 4.A, the monograph by Wayne (1988), and his review article (1994). For compilations of quantum yields of formation and of rate constants for the decay and reactions of 02( A), see Wilkinson et al., 1993 and 1995, respectively. 

Dimerization. Many polycyclic aromatic hydrocarbons form photodimers via 4 + 4 cycloadditions.58-59 Anthracene (11), for example, dimerizes with a limiting quantum yield of 0.3 when irradiated in benzene.59-60 The reaction takes place from the singlet state and competes with fluorescence, which drops to zero at high anthracene concentrations. More detailed coverage of these reactions is found in the reviews by Bowen59 and by Trecker.58... 

For the excited singlet state of rhodamine as product state the free energy plot of the reverse electron transfer from the reduced dye to the hole (dashed curve in Fig. 31) is a mirror image to the free energy plot of the forward reaction relative to AG° =0. We immediately see from Figs. 31 and 32 that this reverse reaction is very fast at phenanthrene and slower at chrysene. It is still slower at anthracene and extremely slow at perylene. At phenanthrene this reverse reaction can compete with the dissociation of the hole from the reduced dye as is borne out by the recombination controlled current in this system (Fig. 27). 

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