Phosphorescence benzene

Table 16 Relative intensities of different vibronic bands in benzene phosphorescence (%).

Vibrational analysis of the benzene phosphorescence bands indicates that the radiative activity is induced predominantly by e2g vibrations [155, 156]. A weak but observable activity of b2g vibrations has also been found [156, 155, 157]. By introducing spin-orbit- and vibronic coupling through second order perturbation theory Albrecht [158] showed that the vibronic interaction within the triplet manifold is responsible for the larger part of the phosphorescence intensity. This also follows from comparison of the vibrational structure in phosphorescence and fluorescence spectra [159]. The benzene phosphorescence spectrum in rigid glasses [155] reveals a dominant vibronic activity of... 

Main mechanisms of benzene phosphorescence. Triplet and Singlet manifolds of states. From ref. [83]. 

I-B Vibronic structure of benzene phosphorescence in the response formalism... 

In a simple harmonic approximation the first term gives the 0-0 band if the transition is allowed for non-distorted symmetrical structure. But in the case of benzene phosphorescence the 3Blu transition is forbidden in Deh symmetry even if the SOC... 

Both types of processes, 7r -assisted y, -bond cleavage and P -bonding, have been invoked to operate in the phototransformations of the aldehyde-ketone (153) to products (155), (156) and (158). The conversions have been observed at room temperature in dioxane, t-butanol, ethanol and benzene using light of wavelengths 2537 A or above 3100 A or sensitization by acetophenone. The phosphorescing excited triple state of (153) is very similar to that of testosterone acetate (114), but its reactions are too rapid... 

Backstrom and Sandros<54-55) found that the phosphorescence of biacetyl in benzene solution at room temperature was quenched at a diffusion-controlled rate by aromatic hydrocarbons when the triplet energy of the hydrocarbon was sufficiently below that of biacetyl. 

El-Sayed 28> has reported on the phosphorescence spectrum of [2.2]paracyclophane. The emission differs both in wavelength ( 4700 A) and in duration (3.3 s) from that of benzene ( 3400 A, 6 s) hence a favorable intersystem crossing from the lowest singlet to the emitting triplet state was inferred. The emission spectrum also indicates that interactions take place between the two aromatic nuclei in the triplet state. 

Fig. 27. Semilogarithmic plot of the nonradiative triplet rate constant against (E— o)/> for the normal and deuterated hydrocarbons listed in Ref. t)). The broken line, derived from phosphorescence spectra, is taken from Ref. t). The slopes of the two solid lines differ by a factor 1.35. (O.Ci-jjH, E = 4000 cm l 0 Ci fl Z>u, =5500 cm t). The following totally deuterated hydrocarbons are included benzene, triphenylene, acenaphtene, naphthalene, phenanthrene, chrysene, biphenyl, p-terphenyl, pyrene, 1,2-benzanthracene, anthracene (in the order of increasing /S). (From Siebrand and Williams, Ref. l)...

Details of nitrobenzene photochemistry reported by Testa are consistent with the proposal that the lowest triplet excited state is the reactive species. Photoreduction, as measured by disappearance quantum yields of nitrobenzene in 2-propanol is not very efficient = (1.14 0.08) 10 2 iD. On the other hand, the triplet yield of nitro benzene in benzene, as determined by the triplet-counting method of Lamola and Hammond 28) is 0.67 0.10 2). This raises the question of the cause of inefficiency in photoreduction. Whereas Lewis and Kasha 29) report the observation of nitrobenzene phosphorescence, no long-lived emission from carefully purified nitrobenzene could be detected by other authors i4,3o). Unfortunately, the hterature value of Et for nitrobenzene (60 kcal mole i) is thus based on an impurity emission and at best a value between 60 and 66 kcal mole can be envisaged from energy-transfer experiments... 

In contrast to borazine, the three corresponding excited singlet states of benzene have a much wider spread of absorbing wavelengths and exhibit easily distinguished vibrational fine structure. Many photolysis experiments have been performed using laser lines tuned to selective excite a particular vibrational level of a particular excited state of benzene. Such experiments are more difficult with borazine. The triplet states of benzene have been located experimentally and quantum yields for fluorescence and phosphorescence at various wavelengths and pressure conditions have been determined. 

The photochemistry of borazine delineated in detail in these pages stands in sharp contrast to that of benzene. The present data on borazine photochemistry shows that similarities between the two compounds are minimal. This is due in large part to the polar nature of the BN bond in borazine relative to the non-polar CC bond in benzene. Irradiation of benzene in the gas phase produces valence isomerization to fulvene and l,3-hexadien-5-ynes Fluorescence and phosphorescence have been observed from benzene In contrast, fluorescence or phosphorescence has not been found from borazine, despite numerous attempts to observe it. Product formation results from a borazine intermediate (produced photochemically) which reacts with another borazine molecule to form borazanaphthalene and a polymer. While benzene shows polymer formation, the benzyne intermediate is not known to be formed from photolysis of benzene, but rather from photolysis of substituted derivatives such as l,2-diiodobenzene ... 

It may be noted that this simple collision process may be complicated by the addition196,200 of a 2-butene to the excited benzene to form a benz-valene-butene adduct.176 The quenching of phosphorescence of organic molecules by oxygen may be explained53,86,140 by the triplet-triplet annihilation mechanism86,129,167... 

Note that although the local permutational symmetry of the 02 molecule remains the same in eq. (5-13), that of the benzene has changed. The change in one local permutational symmetry does not imply the change in another permutational symmetry. Similarly paramagnetic molecules could be expected to enhance phosphorescent emission in some cases. One such example is given by181... 

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