The appearance of the first review in 1965 [1] and the first monograph in 1968 [2] on chemiluminescence demonstrated the extent of the phenomenon of light emission from the reaction of organic compounds in solution. Since then the num ber of chemiluminescent compounds has greatly increased, although the advan ces in theory and, more recently, applications are probably more significant. The present work is written by two authors who, together with E. H. White, helped to bring the study of chemiluminescence into the modern era. However many investigators are making contributions to the subject, even if the number of enthusiasts still remains small. It is not our intention to write an exhaustive account of chemiluminescence, still less of bioluminescence, and we have concentrated on making the landmarks in the area familiar to a readership outside the circle of specialists. The emphasis is on the range of organic compounds showing light emission with very little description of the relatively few inorganic or the more numerous biological examples which have been discovered. We hope that some of the excitement of the striking demonstrations of chemiluminescence which can be made appears in the text, albeit in the form of intellectual satisfaction and interest. We thank Prof. Dr. J. Stauff, Frankfurt for his generous advice and his critical comments. The chapter dealing with Peroxy-oxalate chemiluminescence has been commented up on critically by Dr. M. M. Rauhut, Stamford, Connecticut which we gratefully acknowledge.

InhaltsangabeI. Introduction.- A. Physiochemical Background.- II. General Concepts in Chemiluminescence.- II. 1 Chemiluminescence Efficiency.- II. 1.1 Energetics of the Reactions.- II. 1.2 Formation of the Excited State.- 11.1.2.1 The Reaction Co-ordinate.- 11.1.2.2 Molecular Geometry.- 11.1.2.3 Spin Restrictions.- II. 1.2.4 Symmetry Restrictions.- II. 1.2.5 Potential Energy Surfaces.- II.2 Electron Transfer Reactions.- II. 3 Singlet Oxygen as a Cause of Chemi- and Bioluminescence the Role of Triplet Oxygen.- II. 4 References (for Preface, Chaps. I and II).- B. Chemiluminescent Reactions.- III. Autoxidation Reactions.- III. 1 Hydrocarbons.- III. 1.1 The Excitation Step.- III. 1.2 Polymers.- III. 1.3 Base-catalysed Autoxidation of Carbonyl Compounds.- III. 1.4 Grignard Compounds.- III. 1.5 Inhibitors.- III. 1.6 Miscellaneous Oxidation Reactions.- III. 1.6.1 Oxidative Chemiluminescence of Coals.- III.1.6.2 Cysteine and Glutathione.- III. 2 References.- IV. Chemiluminescent Peroxide Decompositions, I (except Dioxetans).- IV. 1 Peroxide Chemiluminescence by CIEEL.- IV. 2 Acyclic sec. -Peroxy-esters.- IV. 3 Dioxetanones.- IV.4 Diphenoyl Peroxide.- IV.5 Other Cyclic Diacyl Peroxides. Phthaloyl Peroxide.- IV. 6 Chemiluminescence of o-Dicarboxylic Acid Chlorides.- IV.7 Other Cyclic Peroxides.- IV. 8 Acene Endo-Peroxides.- IV.9 Polyhydroxy-phenol- and Purpurogallin Chemiluminescence.- IV. 10 References.- V. Peroxide Decompositions, II: Dioxetans.- V. l Simple Dioxetans.- V.2 Excitation Yields and Multiplicity.- V.3 Measurement of Singlet and Triplet Yields.- V.4 Thermochemistry and Kinetics.- V.5 Mechanism of Excited State Formation from Dioxetans.- V.5.1 The Diradical Mechanism.- V.5.2 The Concerted or Electron Transfer Mechanism.- V. 6 Quenching Reactions of Dioxetans.- V.7 Symmetry Forbidden Reactions in Chemiluminescence.- V. 8 References.- VI. Peroxy Oxalate Chemiluminescence.- VI. 1 Requirements for Oxalate Chemiluminescence.- VI.2 The Mechanism.- VI. 3 References.- VII. Luminol and Related Compounds.- VII. 1 Structure and Activity of Phthalic Acid Hydrazides.- VII. 1.1 Miscellaneous Cyclic Hydrazides.- VII. 1.1.1 Compounds with Multiple Hydrazide Groups.- VII.2 The Emitting Species.- VII.3 Energy Transfer in Luminol Type Chemiluminescence.- VII.4 Solvent Effects.- VII. 5 Effect of Micelle-forming Agents.- VII.6 Catalyst Activity.- VII.7 The Mechanism of Luminol Chemiluminescence.- VII.7.1 Ionic Species Derived from Luminol.- VII.7.2 Diazaquinone Chemiluminescence.- VII.7.3 Intermediate Peroxides.- VII.7.4 1,4-Dialkoxy Phthalazines as Potential Precursors of the Luminol-"endoperoxide".- VII.7.5 Luminol Radical Anions as Intermediates (Pulse Radiolysis Experiments).- VII.7.6 Present State of Hypotheses on Luminol Chemiluminescence Mechanism.- VII.8 Monoacylhydrazides.- VII.8.1 Chemiluminescence Mechanism of Monoacylhydrazides.- VII. 9 References.- VIII. Acridine Derivatives.- VIII. 1 Lucigenin.- VIII. 1.1 The Reaction Mechanism.- VIII.1.2 Energy Transfer in Lucigenin Chemiluminescence.- VIII. 1.3 Influence of Micelle Forming Agents on the Lucigenin Reaction.- VIII.2 Acridinium Salts and Acridans.- VIII. 3 References.- IX. Other Nitrogen-Containing Compounds-Imine Peroxides.- IX. 1 Tetrakis-dialkylaminoethylenes.- IX.2 Bis-Isoquinolinium Salts.- IX.3 Lophine and Related Compounds.- IX.4 Indole Derivatives.- IX.5 Chemiluminescent Schiff Bases.- IX. 6 References.- X. Miscellaneous Compounds.- X. l Chlorinated Cyclic Carbonates, Glycolides and Ethers.- X.2 Sulfuranes.- X.3 Thioesters.- X.4 Vinyl Halides.- X.5 Strained Hydrocarbon Isomerisation.- X.6 Metal Phosphides.- X. 7 References.- XI Electron Transfer Chemiluminescence.- XI. 1 Electrogenerated Chemiluminescence (ECL).- XI.1.1 Energy-sufficient and Energy-deficient ECL.- XI. 1.1.1 Energy-deficient ECL.- XI. 1.2 Chemiluminescent Reactions of Electrogenerated Radical Anions with Organic Halides.- XI. 1.3 Efficiency of ECL Reactions.- XI. 1.4 Ruthenium Chelate Complexes.- XI.2 Chemiluminescent R