Fluorescence from Excited Singlet States

Direct observation of fluorescence from higher singlet states of benzene and some methyl derivatives has recently been achieved by Hirayama, Gregory, and Lipsky (247). Using apparatus capable of detecting fluorescence yields as low as 10 they recorded the emission spectra from oxygenated solutions of pure benzene and other aromatics excited at 184.9 nm. Subtraction of the tail of the residual S, emission gives a fluorescence spectrum with approximately 235 nm and = 8 x 10 for... 

But both the ligand and the lanthanide can also be deactivated. The ligand can emit a photon by fluorescence from its singlet state or by phosphorescence from its triplet state, or can be deactivated (also from either its singlet or triplet excited state) by internal conversion, quenching, or any otiier nomadiative possibility. Even if the sensitization is efficient, i.e., if the isc and et is quick relative to the undesired deactivations, the lanthanide can also experience some nomadiative deactivations, so that the rate of the radiative deactivation of the lanthanide is in competition with nomadiative processes. 

From these and additional results from other compounds of this type it was concluded that the chemiluminescence of (19) and (22) is caused by intramolecular triplet-singlet energy transfer of a mixed dipole-dipole and exchange character. This is demonstrated by the fact that the fluorescence from the singlet-state of the emitter-moiety is not governing the chemiluminescence of these compounds and that, moreover, the most important excited state of the phthalate moieties is the first excited triplet state [38]. Whereas in the compounds (19) and (22) the hydrazide group and the fluorescer group can alter their relative spatial position by (possibly restricted) rotation around the CH2-bonds, this is not possible in paracyclophane-type compounds like (23). 

Typical singlet lifetimes are measured in nanoseconds while triplet lifetimes of organic molecules in rigid solutions are usually measured in milliseconds or even seconds. In liquid media where drfifiision is rapid the triplet states are usually quenched, often by tire nearly iibiqitoiis molecular oxygen. Because of that, phosphorescence is seldom observed in liquid solutions. In the spectroscopy of molecules the tenn fluorescence is now usually used to refer to emission from an excited singlet state and phosphorescence to emission from a triplet state, regardless of the actual lifetimes. 

Figure C 1.5.10. Nonnalized fluorescence intensity correlation function for a single terrylene molecule in p-terjDhenyl at 2 K. The solid line is tire tlieoretical curve. Regions of deviation from tire long-time value of unity due to photon antibunching (the finite lifetime of tire excited singlet state), Rabi oscillations (absorjDtion-stimulated emission cycles driven by tire laser field) and photon bunching (dark periods caused by intersystem crossing to tire triplet state) are indicated. Reproduced witli pennission from Plakhotnik et al [66], adapted from [118].

One characteristic property of dyes is their colour due to absorption from the ground electronic state Sq to the first excited singlet state Sj lying in the visible region. Also typical of a dye is a high absorbing power characterized by a value of the oscillator strength/ (see Equation 2.18) close to 1, and also a value of the fluorescence quantum yield (see Equation 7.135) close to 1. 

Fluorescence from the ExcitedSj State. In Figure 1, after absorption (A) and vibrational deactivation (VD) occur, the lowest or nearly lowest level of the singlet excited state is reached. If the molecule is fluorescent with a high quantum efficiency, fluorescent emission of a quantum of... 

Emission of light due to an allowed electronic transition between excited and ground states having the same spin multiplicity, usually singlet. Lifetimes for such transitions are typically around 10 s. Originally it was believed that the onset of fluorescence was instantaneous (within 10 to lO-" s) with the onset of radiation but the discovery of delayed fluorescence (16), which arises from thermal excitation from the lowest triplet state to the first excited singlet state and has a lifetime comparable to that for phosphorescence, makes this an invalid criterion. Specialized terms such as photoluminescence, cathodoluminescence, anodoluminescence, radioluminescence, and Xray fluorescence sometimes are used to indicate the type of exciting radiation. 

Emission spectra at these points are shown in Figure 8.2d. The band shapes were independent of the excitation intensity from 0.1 to 2.0 nJ pulse . The spectrum of the anthracene crystal with vibronic structures is ascribed to the fluorescence originating from the free exdton in the crystalline phase [1, 2], while the broad emission spectra of the pyrene microcrystal centered at 470 nm and that of the perylene microcrystal centered at 605 nm are, respectively, ascribed to the self-trapped exciton in the crystalline phase of pyrene and that of the a-type perylene crystal. These spectra clearly show that the femtosecond NIR pulse can produce excited singlet states in these microcrystals. 

The acetone-sensitized photodehydrochlorination of 1,4-dichlorobutane is not suppressed by triplet quenchers (20), but the fluorescence of the sensitizer is quenched by the alkyl chloride (13). These observations imply the operation of a mechanism involving collisional deactivation, by the substrate, of the acetone excited singlet state (13,21). This type of mechanism has received strong support from another study in which the fluorescence of acetone and 2-butanone was found to be quenched by several alkyl and benzyl chlorides (24). The detailed mechanism for alkanone sensitization proposed on the basis of the latter work invokes a charge-transfer (singlet ketone)-substrate exciplex (24) and is similar to one of the mechanisms that has been suggested (15) for sensitization by ketone triplets (cf. Equations 4 and 5). 

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