Phosphorescence Excitation Spectroscopy

A number of experimental techniques are available for the determination of triplet energy levels. Those most commonly employed are phosphorescence spectroscopy, phosphorescence excitation spectroscopy, singlet to triplet... 

The very weak Tm - So transitions are hard to observe directly by absorption spectroscopy. Even with long cells, the high concentrations required present solubility — and what is more important — purity problems. An impurity of 1 10 may give rise to absorption bands which have the same intensity as the expected Ti So absorption. The experimental conditions, therefore, have to be chosen to allow an increase of the Ti- - So oscillator strength to be achieved through perturbation by paramagnetic species (O2 or NO) or heavy atoms. Alternatively, an indirect method, phosphorescence excitation spectroscopy, which has high sensitivity and selectivity, may be applied. 

Phosphorescence excitation spectroscopy also allows us to observe the transitions starting at 389 nm to the second triplet state, which is of (n,n ) nature. Direct spin-orbit coupling (mechanism I) to a Sn n,n ) state introduces strong in-plane, long-axis polarization. Indeed, in-plane polarization is preferred over out-of-plane polarization by 3 1, and long-axis polarization is about four times stronger than the short-axis contribution. 

Hirota used doped crystals to observe weak Ti-<- So absorption spectra by phosphorescence excitation spectroscopy. Triplet excitons of the host are formed by direct light absorption. The guest molecules, chosen to have lower triplet energy, act as traps and emit guest phosphorescence. 

Jones, C. R., Kearns, D. R., Wing, R. M. Investigation of singlet-triplet transitions by phosphorescence excitation spectroscopy. X. A simple i, i -unsaturated ketone. J. Chem. Phys. 58, 1370 (1973). 

The properties of the low-lying excited singlet and triplet states of 19 different steroidal enones have been investigated by phosphorescence excitation spectroscopy, at 77 and 4.2 Information was obtained on the ordering of excited... 

When 4>p is independent of the excitation wavelength the extreme sensitivity associated with emission spectroscopy can be utilized to obtain Sg-T absorption spectra by measuring phosphorescence excitation spectra (Mar-chetti and Kearns, 1967). The principle of the method is the same as for... 

The more convenient method of phosphorescence excitation was introduced by Kearns in 1965. Because emission spectroscopy is much more sensitive than absorption, particularly for phosphorescence that can efficiently be separated from stray light and fluorescence, the determination of singlet triplet absorption spectra by monitoring the resulting phosphorescence emission has often been successful with comparatively little effort. 

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. 

The use of emission (fluorescence and phosphorescence) as welt as absorption spectroscopy. From these spectra the presence of as well as the energy and lifetime of singlet and triplet excited states can often be calculated. 

The physical basis of spectroscopy is the interaction of light with matter. The main types of interaction of electromagnetic radiation with matter are absorption, reflection, excitation-emission (fluorescence, phosphorescence, luminescence), scattering, diffraction, and photochemical reaction (absorbance and bond breaking). Radiation damage may occur. Traditionally, spectroscopy is the measurement of light intensity... 

Stabilisers are usually determined by a time-consuming extraction from the polymer, followed by an IR or UV spectrophotometric measurement on the extract. Most stabilisers are complex aromatic compounds which exhibit intense UV absorption and therefore should show luminescence in many cases. The fluorescence emission spectra of Irgafos 168 and its phosphate degradation product, recorded in hexane at an excitation wavelength of 270 nm, are not spectrally distinct. However, the fluorescence quantum yield of the phosphate greatly exceeds that of the phosphite and this difference may enable quantitation of the phosphate concentration [150]. The application of emission spectroscopy to additive analysis was illustrated for Nonox Cl (/V./V -di-/i-naphthyl-p-phcnylene-diamine) [149] with fluorescence ex/em peaks at 392/490 nm and phosphorescence ex/em at 382/516 nm. Parker and Barnes [151] have reported the use of fluorescence for the determination of V-phenyl-l-naphthylamine and N-phenyl-2-naphthylamine in extracted vulcanised rubber. While pine tar and other additives in the rubber seriously interfered with the absorption spectrophotometric method this was not the case with the fluoromet-ric method. 

Nuclear magnetic resonance spectroscopy is a technique that, based on the magnetic properties of nuclei, reveals information on the position of specific atoms within molecules. Other spectroscopic methods are based on the detection of fluorescence and phosphorescence (forms of light emission due to the selective excitation of atoms by previously absorbed electromagnetic radiation, rather than to the temperature of the emitter) to unveil information about the nature and the relative amount specific atoms in matter. 

Among the many excited singlet and triplet levels, 5i and Ti have distinct properties. They are in general the only levels from which luminescence is observed (Kasha rule) also most photochemical reactions occur from Sr or Ti. Here we discuss the characterization of the lowest triplet state by electronic spectroscopy. First we treat the theoretical background that allows the absorption spectra of conjugated systems to be described, and then we discuss the routes that lead to phosphorescence emission and Ti- - Sq absorption intensity. Details of the experimental methods used to determine triplet-triplet and singlet-triplet absorption spectra, as well as phosphorescence emission spectra are given in Chapters III, IV, and V. Representative examples are discussed. 

The new techniques of phosphorescence-microwave multiplet resonance spectroscopy with optical detection have been reviewed by El-Sayed and Kwiram Such exciting experiments as the optical detection on electron-nuclear double resonance (ENDOR) and of electron-electron double resonance (EEDOR) in zero magnetic field have been achieved, and it is certain that much detailed knowledge concerning the phosphorescent states will evolve from this field. 

A number of cyano-bridged complexes are included here even though they strictly do not fall in the general family-type defined for the section. The syntheses and photophysical properties of [(NC)(bpy)2Ru(/r-NC)Cr(CN)5] and [(NC)5Cr(Ai-CI Ru(bpy)2(M-NC)Cr(CN)5] have been described. Absorption of visible light by the Ru(bpy)2 unit results in phosphorescence from the Cr(CN)g luminophore, and the results evidence fast intramolecular exchange energy transfer from the MLCT state of the Ru(bpy)2 chromophore to the doublet state of the Cr -based unit. Time-resolved resonance Raman and transient UV-vis absorption spectroscopies have been employed to investigate the MLCT excited states of [(NC)(bpy)2Ru(//-CN)Ru (bpy)2(CN)], [(NC)(bpy)2Ru(//-CN)Ru(phen)2(CN)]+, [(NC)(phen)2Ru(//-CN)Ru (bpy)2(CN)]+, [(NC)(bpy)2... 

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