Quantum yields compounds

Table 7.16 Fluorescence Spectroscopy of Some Organic Compounds Table 7.17 Fluorescence Quantum Yield Values...

Irradiation of coordination compounds in the charge-transfer spectral region can often enhance redox reactions. The quantum yields are variable. 

Photolytic transformation of diazirines to diazoalkanes was observed in some cases. The parent compound (44) on irradiation in the gas phase with light (A = 3200 A) yields diazomethane. The quantum yield is 0.2 (64JA292). 

For copolymers of structure I, for both types of side-chains, there is a striking similarity with the optical properties of the corresponding models the absorption and photoluminescence maxima of the polymers arc only 0.08-0.09 eV red-shifted relative to those of the models, as shown in Figure 16-9 (left) for the octyloxy-substituted compounds. The small shift can be readily explained by the fact that in the copolymers the chromophorcs are actually substituted by silylene units, which have a weakly electron-donating character. The shifts between absorption and luminescence maxima are exactly the same for polymers and models and the width of the emission bands is almost identical. The quantum yields are only slightly reduced in the polymers. These results confirm that the active chro-mophores are the PPV-type blocks and that the silylene unit is an efficient re-conjugation interrupter. 

The absorption and luminescence spectra of imidazo[ 1,2,4]triazines and related compounds were recorded. The phenyl groups on both the 6-and the 7-positions quenched the luminescence. An acceptor substituent such as CHO in position-7 sharply reduced the luminescence quantum yield (82MI4). A detailed study of the infrared spectra of imidazotriazines was carried out (75T433). 

Quantula (Dyakia), 180, 334 Quantum yield, xvi, 361, 362 aequorin, 104, 106, 110 aldehydes in bacterial bioluminescence, 36, 41 Chaetopterus photoprotein, 224 coelenterazine, 85, 143, 149 Cypridina luciferin, 69-71 definition, xvi, 361 Diplocardia bioluminescence, 242 firefly luciferin, 12 fluorescent compound F, 73 Latia luciferin, 190 pholasin, 197 PMs, 286... 

The acyl phosphonates, acyl phosphine oxides and related compounds (e.g. 81. 82) absorb strongly in the near UV (350-400 nm) and generally decompose by rescission in a manner analogous to the benzoin derivatives.381"285 Quantum yields vary from 0.3 to 1.0 depending on structure. The phosphinyl radicals are highly reactive towards unsaturated substrates and appear to have a high specificity for addition v.v abstraction (see 3.4.3.2). 

Photochemical degradation of brominated dibenzodioxins and fiirans has been studied. Decay of these compounds under environmental conditions is much faster compared to the chlorine analogues due to the higher values for the quantum yields of the bromine compounds. 

Photolysis of all brominated dibenzodioxins investigated occurs very fast in n-hexane. The rate of degradation of all compounds follows a good first-order kinetic scheme. In Table 4 the calculated first order rate constants k are summarised along with the quantum-yields. The corresponding results for three brominated dibenzofurans are also included. 

Between 1923 and 1927, the concepts of quantum efficiency (number of photons emitted divided by number of photons absorbed by a sample) and quantum yield (fraction of excited molecules that emit) had been defined and values determined for many compounds by Vavilov (34). The quantum yield indicates the extent that other energy loss mechanisms compete with emission in an excited molecule. Although the quantum yield is influenced by the molecular environment of the emitter, for a given environment it depends on the nature of the emitting compound and is independent of concentration and excitation wavelength, at least at low concentrations (35). Tlius, it serves as another measurable parameter that can be used to identify the compounds in a sample and also, because of its sensitivity to the surroundings of the luminophore, to probe the environment of the emitter. 

Requirements for standards used In macro- and microspectrofluorometry differ, depending on whether they are used for Instrument calibration, standardization, or assessment of method accuracy. Specific examples are given of standards for quantum yield, number of quanta, and decay time, and for calibration of Instrument parameters. Including wavelength, spectral responslvlty (determining correction factors for luminescence spectra), stability, and linearity. Differences In requirements for macro- and micro-standards are considered, and specific materials used for each are compared. Pure compounds and matrix-matched standards are listed for standardization and assessment of method accuracy, and existing Standard Reference Materials are discussed. 

Calibration. In general, standards used for instrument calibration are physical devices (standard lamps, flow meters, etc.) or pure chemical compounds in solution (solid or liquid), although some combined forms could be used (e.g., Tb + Eu in glass for wavelength calibration). Calibrated lnstr iment parameters include wavelength accuracy, detection-system spectral responsivity (to determine corrected excitation and emission spectra), and stability, among others. Fluorescence data such as corrected excitation and emission spectra, quantum yields, decay times, and polarization that are to be compared among laboratories are dependent on these calibrations. The Instrument and fluorescence parameters and various standards, reviewed recently (1,2,11), are discussed briefly below. 

Solid-surface room-temperature phosphorescence (RTF) is a relatively new technique which has been used for organic trace analysis in several fields. However, the fundamental interactions needed for RTF are only partly understood. To clarify some of the interactions required for strong RTF, organic compounds adsorbed on several surfaces are being studied. Fluorescence quantum yield values, phosphorescence quantum yield values, and phosphorescence lifetime values were obtained for model compounds adsorbed on sodiiun acetate-sodium chloride mixtures and on a-cyclodextrin-sodium chloride mixtures. With the data obtained, the triplet formation efficiency and some of the rate constants related to the luminescence processes were calculated. This information clarified several of the interactions responsible for RTF from organic compounds adsorbed on sodium acetate-sodium chloride and a-cyclodextrin-sodium chloride mixtures. Work with silica gel chromatoplates has involved studying the effects of moisture, gases, and various solvents on the fluorescence and phosphorescence intensities. The net result of the study has been to improve the experimental conditions for enhanced sensitivity and selectivity in solid-surface luminescence analysis. 

Interactions in Solid-Surface Luminescence Temperature Variation. Solid-surface luminescence analysis, especially solid-surface RTF, is being used more extensively in organic trace analysis than in the past because of its simplicity, selectivity, and sensitivity (,1,2). However, the interactions needed for strong luminescence signals are not well understood. In order to understand some of the interactions in solid-surface luminescence we recently developed a method for the determination of room-temperature fluorescence and phosphorescence quantum yields for compounds adsorbed on solid surfaces (27). In addition, we have been investigating the RTF and RTF properties of the anion of p-aminobenzoic acid adsorbed on sodium acetate as a model system. Sodium acetate and the anion of p-aminobenzoic acid have essentially no luminescence impurities. Also, the overall system is somewhat easier to study than compounds adsorbed on other surfaces, such as filter paper, because sodium acetate is more simple chemically. 

R n Compound Number Molar Absorptivity, e X iq3 Fluorescence Quantum Yield, 4> Wavelength of Maximum Absorbance, A. (nm) max... 

Quimtua Yields of Fluorescence Measurements. All of the quantum yields of fluorescence were measured by the relative fluorescence measurement technique of Parker and Rees (24). This method compares the fluorescence of the compound of interest to the fluorescence of some known compound. All of the fluorescence quantum yields were measured using I as a reference. Compound I had previously been measured by this same method using rhodamine B as a standard. 

In the equation, the subscripts 1 and 2 refer to the reference compound and the compound of interest, respectively, is the intensity of the fluorescent signal of each compound measured as peak height in centimeters, 8 is the molar absorptivity, c is the concentration in moles per liter, and is the fluorescence quantum yield. In this application, i is set at 1.00. The concentrations of the solutions that were tested ranged from 10 to 10 M. The solutions run at the higher concentrations were all checked for self-quenching, but none was found. All measurements, except the fluorescence-versus-solvent study, were made in 0.1-N phosphate buffer, pH 7.4. Slit settings on the Perkin-Elmer MPF-2A were 10 mp (nm) for both emission and excitation monochromators. 

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. 

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