Phosphorescence polarization spectrum

The charge transfer and the h,tt states are affected differently by a change in solvent. In polar solvents, the charge transfer state is attained in nonpolar solvents the n,n state results and 4-aminobenzophenone is reduced upon irradiation in cyclohexane.68 This change in chemical reactivity is reportedly paralleled by a change in the phosphorescence emission spectrum.68 This solvent-dependent reactivity, however, is not observed in the photocycloaddition reaction. Irradiation of 4-aminobenzophenone with isobutylene37 in cyclohexane solution failed to produce either the oxetane or the reduction product. The... 

Figure 6.2. (I) Conventional phosphorescence spectrum of 2,3-dichloroquinoxa-line in durene at 1.6°K. (II) am-PMDR spectrum, obtained by amplitude modulation of microwave radiation that pumps the tv-t, (1.055 GHz) zf transition with the detection at the modulation frequency. Only bands whose intensities change upon microwave radiation (1.055 GHz) and thus originate from tv or rz appear in the am-PMDR spectrum. Transitions from r and rv appear with opposite sign (phase-shifted by 180°). (Hb, lie ) Polarization of the am-PMDR spectral transitions, relative to the crystal axes. The band at 0,0-490 cm-1 originates from both the r and t spin states its intensity does not change upon the 1.055-GHz saturation (no band in II) however, its polarization does rhanp. (bands in Hb and IIc ). (Reproduced with permission from M. A. El-Sayed.tt7W)...

II). From this it must be concluded that the long-wavelength absorption of curve I is due to the intra-molecular hydrogen bond of TIN in unpolar solvents as the intensity of this band is reduced in polar solvents (curve II) and disappears completely in the spectrum of MT (without intramolecular hydrogen bond), curve III. Curve IVa represents the fluorescence and IVb the phosphorescence emission of both TIN and MT in... 

The polarized phosphorescence spectra of 1,5-naphthyridine and its d6 isomer in durene and in durene-d14 mixed crystals have been obtained at 4°K. The lowest singlet state is at 27123 and 27200 cm-1, whereas the corresponding triplet state is at 23215 and 23288 cm 1 for the proto and deutero compounds, respectively. The phosphorescence lifetime in durene crystals is 0.23 sec.140 The polarized spectra (4°K) of 1,5-naphthyridine and its d6 isomer in naphthalene have also been examined. There is a difference between the spectra in naphthalene and in durene attributable to a decrease in the strong vibronic coupling that is considered to exist between the n- n state and the higher n -> n states.141 TheEPR spectrum of 1,6-naphthyridine in its lowest triplet state has been observed for solid solutions in single crystals of durene. The nuclear hyperfine structure allows an estimate of 0.14 to be made for the spin density on the nitrogen atom in the 1-position.142... 

Inspection of the data in Table II reveals a bathochromic shift of the of the triplet-triplet absorption with increasing solvent polarity, with a further bathochromic shift when the compound is adsorbed on microcrystalline cellulose. No phosphorescence emission in solution is seen from this compound at room temperature, indicating that the radiative lifetime of this triplet state is long. This is consistent with the lowest energy excited triplet state having predominantly (n, n ) character. The shape of the triplet-triplet absorption spectrum also suggests that this is the case(20). 

Kottis and Lefebvre (322) have suggested that if polarized light is used to excite randomly oriented molecules to the triplet state, observation of the changes in the AMg = +1 ESR spectrum can reveal the correlation of the polarization properties of the excitation with the principal axis system of the triplet zero-field tensor. Such photoselection experiments have been carried out successfully by Lhotse and coworkers (323) and El-Sayed and Siegel (324) on a number of aromatic systems. Piette and collaborators (325) have studied the effect of metal complexation on the zero-field parameters and lifetimes of the phosphorescent triplet of aromatic-metal complexes with similar photoselection technique. The changes in... 

In zf, a number of optical methods can very easily detect the state of spin alignment. The large effects that microwaves have on the phosphorescence spectrum (22), intensity (21), lifetime (39), and polarization (40) give strong indications of the presence of spin-alignment state. 

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. 

The fluorescence polarization excitation spectrum has been measured for thymine in aqueous solution. " The depolarization at the red edge is attributed to the hidden n, ir transition. Ionization of the lowest excited singlet and triplet states have been determined by the effect of pH on the absorption, fluorescence, and phosphorescence spectra of purines and pyrimidines. " Spectral, polarization, and quantum yield studies of cytidylyl-(3, 5 )-adenosine have also been published. Intermediates in the room-temperature flash photolysis of adenine and some of its derivatives have been identified hydrated electron, radical cations and anions, and neutral radicals resulting from their reactions have been assigned. Photoionization occurs via the triplet state. FMN encapsulated in surfactant-entrapped water pools interacts with polar head groups, entrapped water molecules, and outer apolar solvent. ... 

In Figure 5.18 the absorption and emission spectra of azulene are shown. The anomalous fluorescence of azulene from the S, state is easy to recognize. The AP(F) spectrum exhibits a deep minimum at 33,900 cm. The small peak in the absorption spectrum at the same wave number is therefore not due to vibrational structure but rather to another electronic transition, the polarization of which had been predicted by PPP calculations. Figure 5.19 shows all four types of polarization spectra of phenanthrene. FP becomes negative at the vibrational maxima of the fluorescence the most intense vibration is not totally symmetric, in contrast to the one which shows up weakly. For all absorption bands, AP(P) = -0.3. The polarization direction of phosphorescence is perpendicular to the transition moments of all transitions lying in the mo-... 

Polarized phosphorescence spectra of 1,5-naphthyridine 1 (1959MI1, 1973MI2, 1981JSP345) and the ESR spectrum of 1,6-naphthyridine 3 (1975MI1) and hexa-hydro-l,8-naphthyridinetetrazole were recorded (1998MI6). 

The lowest excited triplet state Ti of this crystal belongs, in contrast, only to the anthracene molecule and corresponds to triplet Frenkel excitons with no polar character, as we described in Sect. 6.5. This follows from the energetic position (not shown here) and the vibronic structure of the phosphorescence spectrum [36]. 

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