Elements of Organic Photochemistry

1 Basic Photophysical and Photochemical Concepts.- 1.1. Introduction.- 1.2. Energy Distribution in the Excited Molecule.- 1.2a. Light Absorption.- 1.2b. Internal Conversion and Intersystem Crossing.- 1.2c. Fluorescence and Phosphorescence.- 1.3. Photochemical Kinetics: Concentrations, Rates, Yields, and Quantum Yields.- 1.4. Classification of Molecular Electronic Transitions and Excited States.- 1.4a. ? ? ? Transitions.- 1.4b. n ? ? and l? a? Transitions.- 1.4c. Intramolecular Charge-Transfer Transitions (CT).- Problems.- 2 Photochemical Techniques and the Photodimerization of Anthracene and Related Compounds.- 2.1. Absorption and Emission Spectra.- 2.1a. Transition Probability.- 2.1b. Polarization Spectra.- 2.1c. The Measurement of Fluorescence Spectra and Fluorescence Quantum Yields.- 2.1d. The Measurement of Fluorescence Lifetimes.- 2.2. The Photodimerization of Anthracene and Related Compounds.- 2.2a. Structural Aspects: The Effect of Substituents on the Photodimerization.- 2.2b. Preparative Photochemical Techniques.- 2.2c. Kinetic and Mechanistic Aspects of the Anthracene Photodimerization.- 2.3. The Anthracene Triplet State.- Problem.- References.- 3 Photochemical Techniques and the Photochemistry of Ketones.- 3.1. The Photoreduction of Aryl Ketones: Nature of the Excited State.- 3.2. Flash Photolysis.- 3.3. The Photoreduction of Aryl Ketones: Structural Aspects.- 3.4. The Photoreduction of Aryl Ketones: Secondary Reactions.- 3.5. The Photoreduction of Aryl Ketones: Synthetic Applications.- 3.6. The Photoreduction of Alkanones.- 3.7. Intramolecular Hydrogen Abstraction by Ketones (Type II Cleavage).- 3.7a. The Multiplicity of the Excited State.- 3.7b. Stereoelectronic Effects.- 3.7c. Substituent Effects.- 3.7d. Synthetic Applications.- 3.8. Hydrogen Abstraction by Groups Other Than the Carbonyl.- Problems.- References.- 4 The Photochemistry of Simple Carbonyl Compounds: Type I Cleavage and Oxetane Formation.- 4.1. Type I Cleavage.- 4.1a. The Nature of the Excited State: Part I.- 4.1b. Some Examples and Synthetic Applications of Type I Cleavage Reactions.- 4.1c. Type I Cleavage Reactions Resulting in Loss of Carbon Monoxide.- 4.1d. ?-Cleavage of Cyclopropyl Ketones.- 4.1e. The Nature of the Excited State: Part II.- 4.2. The Formation of Oxetanes from Carbonyls and Olefins.- 4.2a. Oxetane Formation from Olefins and Aryl Ketones and Aldehydes.- 4.2b. Synthetic Applications of Oxetane Formation.- 4.2c. Oxetane Formation from Olefins and Aliphatic Aldehydes and Ketones.- 4.2d. Perturbational Molecular Orbital Theory (PMO) Applied to Oxetane Formation.- Problems.- References.- 5 The Triplet State.- 5.1. Introduction.- 5.1a. The Identity of the Phosphorescent State as a Triplet.- 5.1b. The Definition and Properties of a Triplet State.- 5.2. Determination of Triplet Energy Levels.- 5.2a. Phosphorescence Spectroscopy.- 5.2b. Singlet ? Triplet Absorption Spectra.- 5.2c. Phosphorescence Excitation Spectroscopy.- 5.2d. Flash Photolysis.- 5.2e. Electron Excitation.- 5.2f. The Lowest Triplet Levels of Organic Molecules.- 5.3. Determination of the Efficiency of Intersystem Crossing.- 5.3a. Flash Photolysis.- 5.3b. Triplet-Sensitized Isomerization.- 5.3c. Photooxidation.- 5.3d. Delayed Fluorescence.- 5.3e. Electron Spin Resonance Spectroscopy.- 5.3f. Intersystem Crossing Quantum Yields of Organic Molecules.- 5.4. Determination of Triplet Lifetimes.- 5.4a. Flash Photolysis.- 5.4b. Luminescence Decay.- 5.4c. The Effect of Deuteration on Triplet Lifetime.- 5.4d. Triplet Lifetimes of Various Organic Molecules.- 5.5. Excited State Geometry.- 5.6. Spin-Orbit Coupling and Intersystem Crossing.- 5.6a. The Nature of Spin-Orbit Coupling.- 5.6b. Effect of Heavy Atoms on Intercombinational Transitions in Aromatic Compounds.- 5.6c. Effect of Heavy Atoms on Intercombinational Transitions in Carbonyl and Heterocyclic Compounds.- 5.6d. External Heavy-Atom Effects and Charge Transfer.- References.- 6 Electronic Energy Transfer.- 6.1. Excitation Tran