A
Accuracy, in spectrophosphorimetry, 137, 155, 162, 172, 184
Acenaphthylene, phosphorimetric detec
tion of impurities in, 168 Adsorbates of tryptaflavin, luminescence
of, 52
Air pollution studies, application of phosphorimetry in, 173
Aliphatic ketones, phosphorescence of, 103
Alkaloids
phosphorescence of, 104,188 phosphorimetric determination of, 188 Aminco-Keirs spectrophosphorimeter,
114-116, 125
Amino acids, phosphorescence of, 105 Anabasine
phosphorescence of, 104
phosphorimetric determination in tobacco, 192
Analysis of mixtures, by spectrophos
phorimetry, 138-145 Anthracene
phosphorimetric determination of im
purities in, 159-164
P-type delayed fluorescence of, 53 S-T transition of, 61, 67
Aromatic amines, phosphorescence of, 81 Aromatic carbonyl compounds, phos
phorescence of, 28, 83
Aromatic carboxylic acids, phosphores
cence of, 85 Aromatic hydrocarbons
angular, phosphorescence of, 67, 69 classification of lowest triplet state, 64
with five-membered rings, phosphores
cence of, 68, 71
phosphorescent lifetime of, 36, 76 relationship between phosphores
cence and UV absorption, 75 singlet-triplet splitting in, 66 Aromatic nitro compounds, phosphores
cence of, 28, 81 Aspirin
phosphorescence of, 105, 182 phosphorimetric determination in
blood, 181-185 Azaheterocyclics
in petroleum products, analysis of, 175
spectroscopic characterization of, 174 Azapyrene, phosphorescence of, 95 Azulene, fluorescence of, 18
Β
Becquerel phosphoroscope, 112 Benzanthracene, phosphorimetric detec
tion of impurities in, 168 Benzene
assignment of the S-T transition, 60 phosphorescence spectrum of, 30, 59,
67
phosphorescent lifetime of, 76 singlet-triplet absorption of, 7, 60 Benzocarbazoles, phosphorescence of,
96,100
Benzodiphenylene oxides, phosphores
cence of, 100,101
Benzodiphenylene sulfides, phosphores
cence of, 100, 101
Benzophenone, use as solvent in phos
phorescence spectroscopy, 122 Benzoquinolines, phosphorescence of,
92, 94
Benzoquinone, triplet state of, 89 Benzoquinoxaline, phosphorescence of,
92, 94
Benzpyrene, phosphorimetric detection of impurities in, 167
Biacetyl, phosphorescence of, 11,103 Biphenyl, phosphorimetric determina
tion in oranges, 189-191
Boric acid, use as solvent in phosphores
cence spectroscopy, 120
Butadiene, singlet-triplet absorption of, 102
C
Carbazole, phosphorescence of, 31, 96, 100
Catalase, phosphorescence of, 106 Cell arrangement, in phosphorescence
spectrometers, 110
Charge-transfer complexes, luminescence of, 26
Chelates of dibenzoylmethane, phos
phorescence of, 23
Chlorophyll, phosphorescence of, 106 Chymotrypsin
phosphorescence of, 106
phosphorimetric determination of, 180 Coal tar fractions, phosphorimetric
analysis of, 169-173
Codeine, phosphorescence of, 104, 188 Condensed polyphenyls, phosphores
cence of, 68, 71-75 Coronene
Ε-type delayed fluorescence of, 52 phosphorescence of, 32, 68, 70
D
Deoxyribonucleic acid, phosphorescence of, 105
Detector systems, in phosphorescence spectrometers, 113
Dibenzanthracene, phosphorimetric detection of impurities in, 167
Dibenzocarbazole, phosphorescence of, 97, 99
Dibenzoquinoxalines, phosphorescence of, 92
Dinitronaphthalenes, phosphorescence of, 81
Dinucleotides, triplet energy transfer in, 105
Diphenylene oxide, phosphorescence of, 100,101
Diphenylene sulfide, phosphorescence of, 100,101
Drugs
phosphorescence of, 187
phosphorimetric determination in blood or urine, 185
Ε Eosin, luminescence of, 11, 50 EPA
composition of, 117 purification of, 118
volume contraction on cooling, 119 Estimation of compounds, by spectro
phosphorimetry, 132-137, 142 Ethylene, singlet-triplet absorption of,
102
Ε-Type delayed fluorescence, 50 of dyes, 51
excitation mechanism, 49
Excitation wavelength, in spectrophos
phorimetry, choice of, 124,139,164, 170
F
Ferrocene, phosphorescence of, 39 Flash spectroscopy, 44
Fluorene, phosphorimetric detection of impurities in, 166
Fluorescence mechanism of, 10 of «-7r*-type, 90
Formaldehyde, singlet-triplet absorption of, 103
G
Gas chromatography, combined applica
tion of spectrophosphorimetry and, 148, 175
Glassy plastics, use as solvents in phos
phorescence spectroscopy, 119 Glyoxal, S-T transition of, 103
H
Halogenoanthracenes, phosphorescence of, 79, 80
Halogenobenzenes, S-T transition of, 7, 80
Halogenonaphthalenes, phosphores
cence of, 15, 19, 22, 24, 40, 78, 80 Heavy atom effect
definition of, 21 external
of alkyl halides, 24, 122, 128,130 application in spectrophosphori
metry, 122, 130, 143, 153, 170 influence on phosphorescent life
time, 24, 128
on singlet-triplet absorption, 25 on vibrational structure of phos
phorescence spectra, 31-33,131 of rare gases, 25
internal
influence on phosphorescence quan
tum yield, 22
on phosphorescent lifetime, 14,22 on singlet-triplet absorption, 7,22 Heptacene-7,16-quinone, fluorescence
of, 86
Hexacene-6,15-quinone, fluorescence of, 86
High-temperature phosphorescence, see Ε-Type delayed fluorescence Homologs of aromatic hydrocarbons,
phosphorescence of, 77 Hund's rule, 27
I
Identification of compounds, in spectro
phosphorimetry, 129, 130, 138, 141 Iminophenanthrene, phosphorescence of,
98, 100
Impurities in polycyclic aromatic hydro
carbons, phosphorimetric evalua
tion of, 158-168 Indole
derivatives, of biochemical interest, phosphorescence of, 181
phosphorescence of, 96
Inhibitors, in polymers, phosphorimetric determination of, 178
Inner filter effects, in spectrophosphori
metry, 111, 135, 160 Intercombination restriction, 5 Internal conversion, definition of, 9 Intersystem crossing
definition of, 9
between states of different orbital character, 90
of same orbital character, 90 Ionization energy, relationship to S-T
transition in aromatic hydrocarbons, 62
Isoquinoline, phosphorescence of, 91, 94 J
JJ coupling, 4, 6
Κ
Kasha's rule, 17 L
Lanthanides, sensitized phosphorescence of, 48
Limits of detection
comparison between spectrophos
phorimetry and spectrofluorimetry, 151
Limits of detection—cont.
by phosphorimetry alkaloids, 154, 188 amino acids, 154
aromatic carbonyl compounds, 154 aromatic hydrocarbons, 152, 154 aromatic Ν compounds, 154 drugs, 154, 187
in spectrophosphorimetry, 137, 150- 154
Lycopene, phosphorescence of, 102
M
Mean phosphorescent lifetime
analytical applications of, 128, 141, 165
definition of, 33
dependence on temperature, 37 measurement of, 127
of various compounds, 36
Mercury vapor lamps, use in phos
phorescence spectrometers, 109 Methylcoronene, phosphorescence of, 78 Monochromators, use in phosphores
cence spectrometers, 110
Morphine, phosphorescence of, 104,188
Ν
Ν Analogs of anthracene, S-T transitions of, 93
Naphthalene
sensitized phosphorescence of, 45, 47 S-T transition of, 61,67
Natural phosphorescent lifetime definition of, 33
estimation from S-T absorption, 35 Nicotine
phosphorescence of, 104
phosphorimetric determination in tobacco, 192
Nitroanilines, luminescence of, 82 Nitronaphthylamines, luminescence of,
82
Nornicotine
phosphorescence of, 104
phosphorimetric determination in tobacco, 192
Ο
Orotic acid, photochemical dimerization of, 105
Ρ Paper chromatography
in air pollution studies, 147
of biologically important substances, 147
of coal tar fractions, 147
combined application of spectrophos
phorimetry and,146-148 Pepsin, phosphorescence of, 106 Perdeuterated hydrocarbons, phosphor
escent lifetime of, 34
Perylene, delayed fluorescence of, 56 Pesticides, phosphorimetric determina
tion of, 191 Phenanthrene
P-type delayed fluorescence of, 53 S-T transition of, 31, 63, 67
use as solvent in phosphorescence spectroscopy, 120
Phenanthrolines, phosphorescence of, 92, 94
Phenazine, phosphorescence of, 93 Phenes, phosphorescence of, 63, 67 Phenols, phosphorescence of, 81
*p# „ 2 1 , 3 9
measurement of, 129 of various compounds, 130 Phosphorescence
in crystalline aliphatic hydrocarbon matrix, 30
of crystals, 18 excitation spectra, 126
experimental conditions for measuring spectra, 123-126
in gaseous state, 11
Phosphorescence—cont.
in liquid solutions, 11 mechanism of, 10
«-π*, properties of, 28, 91,121
7 Γ - 7 Γ * , properties of, 28, 91, 121 sensitized, 45,123
vibrational structure of spectra, 29-33 Phosphorescence decay curves, arrange
ments for measuring, 116,127 Phosphorescence intensity, dependence
on concentration of phosphorescent compound, 132-136
Phosphorescence spectrometers calibration of, 126
general description, 109,113 with high sensitivity, 114 Phosphoroscopes, 112
Phthalocyanines, luminescence of, 24 Polarization of phosphorescence
aromatic heterocyclics, 42 aromatic hydrocarbons, 41 arrangements for measuring, 116 connection with singlet-triplet mixing,
29, 40
halogenonaphthalenes, 40
heterocyclics with η-π*-phosphores
cence, 42
nature of pertubing singlet state, 42 Polyacetylenes, phosphorescence of,
102
Procaine, phosphorescence of, 105, 186
Progesteron, phosphorescence of, 106 Proteins, phosphorescence of, 106 P-type delayed fluorescence, 54
of aromatic hydrocarbons in vapor state, 54
excitation mechanism, 52 experimental criteria, 53 of mixed crystals, 55 sensitized, 55, 155
analytical applications of, 155-157 Purines, phosphorescence of, 106 Purity, criteria of, in spectrophosphori
metry, 124, 128
Pyrazine, phosphorescence of, 89
Pyrene
benzologs and, phosphorescence of, 68, 70
phosphorimetric detection of im
purities in, 164-166 Pyridine, S-T absorption of, 89 Pyrimidine, phosphorescence of, 89
Q Quantum spectra, 125
Quantum yield of phosphorescence arrangements for measuring; 116 dependence on excitation wavelength,
39
on temperature, 38 determination of, 38 of various compounds, 38
Quenching, in spectrophosphorimetry, 137
Quinoline
hydrogénation of, analytical character
ization of products, 177 luminescence of, 91, 94 Quinones
lowest 7Γ-7Γ* triplet state of, 18, 88 luminescence behavior of, 85 singlet-triplet splitting in, 68
R
Radiationless transitions, description of, 8
Radiationless triplet energy transfer definition of, 44
dependence on concentration, 48 in dinucleotides, 105
intramolecular, 46 in mixed crystals, 46 Right angle method, 110 Rigid solvents, 12, 117-119
connection between polarity and phosphorescence behavior, 91,121 Russel-Saunders coupling, 4
S
Selectivity, of spectrophosphorimetry, 150
Singlet-singlet transitions, characteristics of, 5
Singlet state, definition of, 3
Singlet-triplet absorption spectra, 7, 15, 25
oxygen effect on, 25, 84 Singlet-triplet splitting, 29, 65 Singlet-triplet transitions
characteristics of, 7
quantum mechanical description of, 5 Solvents, for phosphorimetry, 117-123 Specimen tubes, for phosphorescence
measurements, 111
Spectrofluorimetry, comparison with spectrophosphorimetry, 149 Spin-orbit coupling, 6,14, 20 Spin-orbit coupling effects
external, definition of, 21 internal, definition of, 21
Steric effects, in phosphorescence, 78,102 Straight-through method, 111
Symmetry prohibition, in phosphores
cence, 30
Τ Tetracene
phosphorimetric detection of impuri
ties in, 168
S-T transition of, 62, 67
Tetracene-5,12-quinone, phosphores
cence of, 88
Thebaine, phosphorescence of, 104, 188 Thin-layer chromatography
combined application of spectro
phosphorimetry and, 148, 174, 190, 194
Thionaphthene, S-T transition of, 99 .yym-Triazine, phosphorescence of, 90 Trichlorobenzene, use as solvent in
phosphorescence spectroscopy, 120 Triplet state
definition of, 3
ESR measurements on, 13 lowest, classification of, 29 paramagnetism of, 13
quantum mechanical calculation of, 15 radiationless deactivation of, 12, 34 Triplet-triplet absorption spectra, 43 Triplet-triplet annihilation, 54 Triplet-triplet fluorescence, 18
U
UV absorption spectroscopy, compari
son with spectrophosphorimetry, 149
X
Xenon lamps, use in phosphorescence spectrometers, 109
