Phosphorescence triplet states interactions

Spectroscopists observed that molecules dissolved in rigid matrices gave both short-lived and long-lived emissions which were called fluorescence and phosphorescence, respectively. In 1944, Lewis and Kasha [25] proposed that molecular phosphorescence came from a triplet state and was long-lived because of the well known spin selection rule AS = 0, i.e. interactions with a light wave or with the surroundings do not readily change the spin of the electrons. 

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. 

Some tryptophans do not exhibit phosphorescence because of quenching by specific sites from within the protein. The absence of phosphorescence could be due to quenching of either the singlet state or the triplet state. For example, in horse heart cytochrome c the tryptophan is adjacent to the heme, and its fluorescence is quenched by Forster transfer to the heme. Since the singlet state is populating the triplet state, the lack of observable phosphorescence is likely to be due to an unpopulated triplet state. Another example where the redox center of the protein interacts with the tryptophan excited states is found in azurin. The copper(II) quenches both the singlet and triplet states.(28)... 

The lowest excited states of paramagnetic metal complexes are described by configuration interactions of the porphyrin (7T,tt ) excited singlet and triplet states and the "porphyrin-to-metal" or metal-to-porphyrin charge-transfer excited states (35,36). Thus T (phosphorescence) emission of paramagnetic metal complexes decays... 

Hutchison reported the first ESR spectrum of a metastable phosphorescent state by study of naphthalene oriented in durene crystals.4 Since then, similar spectra have been recorded for several other polynuclear aromatics both oriented in host crystals and randomly suspended in glassy matrices. D values for all these ir,n excited states are quite low, indicating little interaction between the unpaired electrons. Interestingly, D for the quinolines equals 0.10cm"1 just as in naphthalene,197 indicating that the presence of a heteroatom does not necessarily change the ir,w nature of the lowest triplet state very much. A similar conclusion has been reached from a comparison of the ESR spectra of fluorene, carbazole, dibenzofuran, and dibenzothiophene.198... 

Furthermore, the electron can go from S, to a triplet state through an intersystem crossing. From the triplet state the electron can in principle only decay by a non-radiative process back to the ground state S0. Nevertheless, spin-orbit coupling of the electrons and magnetic interactions can allow a weak phosphorescence process from Tj to S0. 

Exciplex phosphorescence can be studied with complexes which are present in the ground state [118]. Equation (43) and its corollaries with respect to variations in A are applicable also to exciplex phosphorescence. For example, positive deviations (A > 0.18 eV) which have been found in the phosphorescence of complexes with (E — E d) > 2.75 eV are ascribed to the stabilizing interaction between the triplet CT state and energetically higher locally excited triplet states [108,119],... 

A. Important Developments in Triplet-State Research Active studies on the relationship between phosphorescence and the lowest triplet state started in the 1940s by G. N. Lewis and his group (la-lf). In the 1950s and 1960s the electric dipole radiation of the phosphorescence was shown to result from spin-orbit interaction by demonstrating heavy atom effects on the emission... 

It should be pointed out that once the zf origin of the different bands is determined (in particular the true and false origins of the spectrum), a complete description could be given for the spin-orbit perturbations that give the lowest triplet state its radiative properties. A very extensive work was conducted by Tinti and El-Sayed (39) in which different perturbations—e.g., heating, applying a magnetic field, as well as saturation of the zf transitions with microwave radiation-were used to determine the property of the individual zf levels. The effect of these perturbations not only on the phosphorescence spectrum but also on the observed decays and polarizations has been examined. Limits on the importance of the different spin-orbit interactions are obtained. This spectroscopic work represents the type of experiments that can be done and the kind of information that can be obtained from PMDR and other methods. 

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