Photochemistry and Photophysics Concepts, Research, Applications. V. Balzani, Paolo Ceroni e Alberto Jurin. Wiley VCH. Preface

Transcription

1 Photochemistry and Photophysics Concepts, Research, Applications V. Balzani, Paolo Ceroni e Alberto Jurin Wiley VCH Preface Chapter 1. Introduction 1.1 Photochemistry and photophysics in science and technology 1.2. Historical notes 1.3 A new dimension of Chemistry and Physics 1.4 The nature of light 1.5 Absorption of light 1.6 Quantum yield, efficiencies and excited state reactivity Chapter 2. Elementary Molecular orbital theory 2.1 The hydrogen atom 2.2 Polyelectronic atoms 2.3 From atoms to molecules 2.4 Electronic structure of homonuclear diatomic molecules 2.5 Electronic structure of heteronuclear diatomic molecules 2.6 Simple polyatomic molecules Elements of group theory Water Ammonia 2.7 Typical organic molecules Methane Ethene Benzene Formaldehyde 2.8 Transition metal complexes

2 2.8.1 General concepts Typical metal complexes BOX 2.1 Group theory BOX 2.2: Nd 3+ complexes Chapter 3. Light absorption and excited state deactivation) 3.1 Light absorption Selection rules Symmetry selection rules Spin selection rules The Franck-Condon Principle Visualization of photochemical reactions on potential energy surfaces 3.2 Jablonski diagram 3.3 Excited state deactivation Vibrational relaxation Radiationless deactivation Radiative deactivation Radiative lifetime 3.4 Chemical reactions 3.5 Kinetic aspects 3.6 Solvent and temperature effects Solvatochromic shift Crossing of states Temperature effect on excited state lifetime Thermally-activated delayed fluorescence 3.7 Selected molecules Oxygen Naphthalene Benzophenone Zinc(II)tetraphenylporphyrin [Cr(en) 3 ] [Co(NH 3 ) 6 ] 3+

3 3.7.7 [Ru(bpy) 3 ] 2+ BOX 3.1: Multiphoton processes BOX 3.2: Solvatochromic dyes BOX 3.3: Quantum dots Chapter 4. Excited states: physical and chemical properties 4.1 Excited state as a new molecule 4.2 Lifetime 4.3 Energy 4.4 Geometry Small molecules Ethene Ethine Benzene Formaldehyde Square planar metal complexes 4.5 Dipole moments 4.6 Electron transfer 4.7 Proton transfer 4.8 Excimers and exciplexes Chapter 5. From molecules to supramolecular systems 5.1 Supramolecular (multicomponent) systems and large molecules 5.2 Electronic interaction in mixed-valence compounds 5.3 Electronic interaction in donor-acceptor complexes 5.4 Electronic stimulation and electronic interaction in the excited state 5.5 Excimers and exciplexes formation in supramolecular systems BOX 5.1: On emission quantum yield in supramolecular systems DA FARE Chapter 6. Quenching and sensitization processes in molecular and supramolecular species 6.1 Introduction 6.2 Bimolecular quenching

4 6.2.1 Stern-Volmer equation Kinetic details Static vs dynamic quenching Sensitized emission quantum yield Spin considerations 6.3 Triplet-triplet annihilation Delayed fluorescence Energy up-conversion 6.4 Quenching within supramolecular systems 6.4 Electron transfer Marcus Theory Quantum Mechanical Theory The Electronic Factor The Nuclear Factor Optical Electron Transfer 6.5 Energy transfer Coulombic Mechanism Exchange Mechanism 6.6 Role of the Bridge in supramolecular systems 6.7 Catalyzed deactivation BOX 6.1: Photocatalysis Chapter 7. Molecular organic photochemistry 7.1 Introduction 7.2. Alkenes and related compounds Basic concepts Photoisomerization of double bonds Electrocyclic processes Sigmatropic rearrangements Di-π-methane reactions Photocycloaddition reactions Photoinduced nucleophile, proton and electron addition 7.3. Aromatic compounds

5 7.3.1 Introduction Photosubstitution Photorearrangement Phototransposition Photocycloadditions 7.4. Carbonyl compounds Introduction Photochemical primary processes 7.5. Photochemistry of other organic compounds Nitrogen compounds Overview Photoisomerization of azocompounds Saturated oxygen and sulfur compounds Halogen compounds BOX 7.1 Singlet oxygen BOX 7.2: Solid state photochemistry Chapter 8. Photochemistry and photophysics of metal complexes 8.1 Metal complexes 8.2 Photophysical properties: general concepts 8.3 Photochemical reactivity: general concepts 8.4 Relationships between electrochemistry and excited state properties Cobalt (III) complexes Copper(I) complexes Electrochemical properties of [Ru(bpy) 3 ] Excited state redox potentials 8.5 Luminescent metal complexes Polypyridine metal complexes Cyclometallated complexes Ruthenium complexes Rhodium complexes Iridium complexes Platinum complexes Orbital nature of the emitting excited state

6 8.5.3 Porphyrine complexes Chromium(III) complexes Lanthanide complexes 8.6 Photochemical processes Photodissociation and related reactions Photooxidation-reduction reactions Intramolecular rearrangements Box 8.1 Oxidative addition of Pt(II) complexes Box 8.2 Identification of the reactive excited state in Cr(III) complexes by sensitization and quenching Box 8.3 Spin crossover in [Fe(bpy) 3 ] 2+ Chapter 9. Interconversion of light and chemical energy by bimolecular redox processes 9.1 Light as a reactant 9.2 Light as a product 9.3 Conversion of light into chemical energy 9.4 Chemiluminescence 9.5 Electrochemiluminecence 9.6 Light absorption sensitizers 9.7 Light emission sensitizers Chapter 10. Light-powered molecular devices and machines 10.1 Molecules, self-organization and covalent synthetic design 10.2 Light inputs and outputs: reading, writing and erasing 10.3 Molecular devices for information processing Photochromic systems as molecular memories Molecular logics Luminescence sensors as simple logic gates AND logic gate XOR logic gate with an intrinsic threshold mechanism Encoding and decoding 10.4 Molecular devices based on energy transfer

7 Wires Switches Plug/socket systems Light-harvesting antennas 10.5 Molecular devices based on electron transfer Wires Switches Extension cable 10.6 Light powered molecular machines Basic remarks The role of light Rotary motors based on cis-trans photoisomerization Linear motions: molecular shuttles and related systems Photocontrolled valves, boxes and related systems Chapter 11. Natural and Artificial Photosynthesis 11.1 Energy for spaceship Earth 11.2 Natural photosynthesis Light harvesting: absorption and energy transfer Photoinduced electron transfer leading to charge separation Bacterial photosynthesis Green plants photosynthesis: Photosystem II Efficiency of photosynthesis 11.3 Artificial photosynthesis Artificial antenna Artificial reaction centers Coupling artificial antenna and reaction center Coupling one-photon charge-separation with multi-electron water splitting 11.4 Water splitting by semiconductor photocatalysis BOX 11.1: Giacomo Ciamician: a pioneer of photochemistry BOX 11.2: The Science of leaf color change BOX 11.3: Evaluation of catalyst efficiency in photocatalytic process BOX 11.4: Artificial photosynthesis versus photovoltaics

8 Chapter 12 Experimental techniques 12.1 Apparata Light sources Monochromators, filters and solvents Cells and irradiation equipment Detectors 12.2 Steady state absorption and emission spectroscopy Absorption spectroscopy Qualitative and quantitative applications Sample measurement Emission spectroscopy Instrumentation Emission spectra Excitation spectra Presence of spurious bands Quantitative relationship between luminescence intensity and concentration Stern-Volmer luminescence quenching Emission quantum yields 12.3 Time-resolved absorption and emission spectroscopy Transient absorption spectroscopy Transient absorption with nanosecond resolution Transient absorption with femtosecond resolution Emission lifetime measurements Single flash Gated sampling Single photon counting Data analysis Phase shift Luminescence lifetime standards 12.4 Absorption and emission measurements with polarized light Linear dichroism Luminescence anisotropy 12.5 Reaction quantum yields and actinometry Reaction quantum yields Actinometry Potassium ferrioxalate Potassium reineckate Azobenzene 12.6 Other techniques Photothermal methods Photoacoustic spectroscopy Photorefractive spectroscopy

9 Single molecule spectroscopy Fluorescence correlation spectroscopy X-ray techniques BOX 12.1 Lasers Chapter 13. Light and life 13.1 Introduction 13.2 Vision Basic principle Primary photochemical events 13.3 Sunscreens 13.4 Photochemical damage in living systems Photochemical damage to DNA Photochemical damage to Proteins 13.5 Therapeutic strategies using light Phototherapy Photochemotherapy of psoriasis Photodynamic therapy Photocontrolled delivery 13.6 Photocatalysis in environmental protection Principles Solar disinfection (SODIS) Photo-assisted Fenton reaction Heterogeneous photocatalysis 13.7 DNA photocleavage and charge transport Photocleaving agents of nucleic acid Photoinduced electron transfer processes in DNA 13.8 Fluorescence 13.9 Bioluminescence Chapter 14. Technological applications of photochemistry and photophysics 14.1 Introduction 14.2 Photochromism

10 14.3 Luminescence sensors Principles Amplifying signal Wind tunnel research Thermometers Measuring blood analytes Detecting warfare chemical agents Detecting explosives 14.4 Optical brightening agents 14.5 Atmospheric photochemistry Natural processes involving oxygen Ozone hole 14.6 Solar cells Inorganic photovoltaic (PV) cells Organic solar cells (OSCs) Dye-sensitized solar cells (DSSCs) 14.7 Electroluminescent materials Light-emitting diodes (LEDs) Organic Light-emitting diodes (OLEDs) Light-emitting electrochemical cells (LECs) 14.8 Polymers and light Photopolymerization Photodegradation Stabilization of commercial polymers Photochemical curing Other light-induced processes Photolitography Stereolithography Holography 14.9 Light for chemical synthesis Photochlorination of polymers Synthesis of caprolactam Synthesis of vitamins Perfumes

11 Chapter 15. Green (photo)chemistry 15.1 Definition, origins and motivations 15.2 Photochemistry for green chemical synthesis 15.3 Photocatalysis Heterogeneous photocatalysis Homogeneous photocatalysis 15.4 Photocatalysis in synthesis Alkanes Alkene Alkynes Sulfides 15.5 Photocatalytic pollution remediation 15.6 Use of solar energy in green synthesis Chapter 16. Research frontiers 16.1 Introduction 16.2 Aggregation-induced emission 16.3 Phosphorescence from purely organic materials by crystal design 16.4 Synthesis of a 2-D polymer 16.5 Photocontrolled unidirectional transit of an asymmetric molecular wire through a molecular ring 16.6 Molecular rotary motors powered by visible light via energy transfer 16.7 Cooperation and interference in multifunction compounds 16.8 Singlet fission 16.9 One-color photochromic system Photonic Modulation of Electron Transfer with Switchable Phase Inversion Dye-sensitized photoelectrosynthesis cells (DSPECs)

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