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Photochemistry and Photophysics - Concepts,       Research, Applications

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Home » Books » Science » Chemistry » Industrial & Technical

Photochemistry and Photophysics - Concepts, Research, Applications

By Vincenzo Balzani, Paola Ceroni, Alberto Juris

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Format: Paperback, 504 pages
Other Information: Illustrated
Published In: Germany, 01 June 2014
This textbook covers the spectrum from basic concepts of photochemistry and photophysics to selected examples of current applications and research. Clearly structured, the first part of the text discusses the formation, properties and reactivity of excited states of inorganic and organic molecules and supramolecular species, as well as experimental techniques. The second part focuses on the photochemical and photophysical processes in nature and artificial systems, using a wealth of examples taken from applications in nature, industry and current research fields, ranging from natural photosynthesis, to photomedicine, polymerizations, photoprotection of materials, holography, luminescence sensors, energy conversion, and storage and sustainability issues. Written by an excellent author team combining scientific experience with didactical writing skills, this is the definitive answer to the needs of students, lecturers and researchers alike going into this interdisciplinary and fast growing field.

Table of Contents

List of Boxes XVII Preface XIX Acknowledgments XXV List of Abbreviations XXVII 1 Introduction 1 1.1 Photochemistry and Photophysics in Science and Technology 1 1.2 Historical Notes 2 1.3 A New Dimension of Chemistry and Physics 3 1.4 The Nature of Light 5 1.5 Absorption of Light 7 1.6 Quantum Yield, Efficiencies, and Excited-State Reactivity 8 References 10 2 Elementary Molecular Orbital Theory 11 2.1 Introduction 11 2.2 The Hydrogen Atom 11 2.3 Polyelectronic Atoms 13 2.4 From Atoms to Molecules 17 2.5 Electronic Structure of Homonuclear Diatomic Molecules 21 2.6 Electronic Structure of Heteronuclear Diatomic Molecules 25 2.7 Simple Polyatomic Molecules and Elements of Group Theory 26 2.7.1 Elements of Group Theory 26 2.7.2 Water 29 2.7.3 Ammonia 31 2.8 Typical Organic Molecules 33 2.8.1 Methane 33 2.8.2 Ethene 35 2.8.3 Benzene 37 2.8.4 Formaldehyde 39 2.9 Transition Metal Complexes 41 2.9.1 General Concepts 41 2.9.2 Typical Metal Complexes 48 References 52 3 Light Absorption and Excited-State Deactivation 55 3.1 Light Absorption 55 3.1.1 Selection Rules 57 3.1.2 Symmetry Selection Rules 58 3.1.3 Spin Selection Rules 59 3.1.4 The Franck?Condon Principle 60 3.1.5 Visualization of Photochemical Reactions on Potential Energy Surfaces 62 3.2 Jablonski Diagram 64 3.3 Excited-State Deactivation 68 3.3.1 Vibrational Relaxation 68 3.3.2 Radiationless Deactivation 68 3.3.3 Radiative Deactivation 71 3.3.4 Radiative Lifetime 72 3.4 Chemical Reactions 73 3.5 Kinetic Aspects 74 3.6 Solvent and Temperature Effects 75 3.6.1 Solvatochromic Shift 75 3.6.2 Crossing of States 77 3.6.3 Temperature Effects on Excited-State Lifetime 79 3.6.4 Thermally Activated Delayed Fluorescence 80 3.7 Selected Molecules 81 3.7.1 Oxygen 81 3.7.2 Naphthalene 83 3.7.3 Benzophenone 85 3.7.4 Zinc(II) Tetraphenyl Porphyrin 87 3.7.5 [Cr(en)3]3+ 90 3.7.6 [Co(NH3)6]3+ 92 3.7.7 [Ru(bpy)3]2+ 94 3.8 Semiconductors 96 References 100 4 Excited States: Physical and Chemical Properties 103 4.1 Excited State as a New Molecule 103 4.2 Lifetime 103 4.3 Energy 104 4.4 Geometry 105 4.4.1 Small Molecules 106 4.4.2 Ethene 107 4.4.3 Ethyne 108 4.4.4 Benzene 109 4.4.5 Formaldehyde 109 4.4.6 Square Planar Metal Complexes 111 4.5 Dipole Moments 112 4.6 Electron Transfer 114 4.7 Proton Transfer 117 4.8 Excimers and Exciplexes 120 References 122 5 From Molecules to Supramolecular Systems 125 5.1 Supramolecular (Multicomponent) Systems and Large Molecules 125 5.2 Electronic Interaction in Mixed-Valence Compounds 127 5.3 Electronic Interaction in Donor?Acceptor Complexes 129 5.4 Electronic Stimulation and Electronic Interaction in the Excited State 131 5.5 Formation of Excimers and Exciplexes in Supramolecular Systems 134 References 136 6 Quenching and Sensitization Processes in Molecular and Supramolecular Species 139 6.1 Introduction 139 6.2 Bimolecular Quenching 140 6.2.1 Stern?Volmer Equation 140 6.2.2 Kinetic Details 143 6.2.3 Static versus Dynamic Quenching 144 6.2.4 Sensitized Processes 145 6.2.5 Spin Considerations 146 6.3 Quenching and Sensitization Processes in Supramolecular Systems 146 6.4 Electron-Transfer Kinetics 150 6.4.1 Marcus Theory 150 6.4.2 Quantum Mechanical Theory 153 6.4.2.1 The Electronic Factor 154 6.4.2.2 The Nuclear Factor 156 6.4.2.3 Optical Electron Transfer 156 6.5 Energy Transfer 157 6.5.1 Coulombic Mechanism 159 6.5.2 Exchange Mechanism 161 6.6 Role of the Bridge 163 6.7 Catalyzed Deactivation 164 References 166 7 Molecular Organic Photochemistry 169 7.1 Introduction 169 7.2 Alkenes and Related Compounds 169 7.2.1 Basic Concepts 169 7.2.2 Photoisomerization of Double Bonds 170 7.2.3 Electrocyclic Processes 172 7.2.4 Sigmatropic Rearrangements 173 7.2.5 Di-?-Methane Reaction 174 7.2.6 Photocycloaddition Reactions 174 7.2.7 Photoinduced Nucleophile, Proton, and Electron Addition 175 7.3 Aromatic Compounds 176 7.3.1 Introduction 176 7.3.2 Photosubstitution 179 7.3.3 Photorearrangement 180 7.3.4 Phototransposition 181 7.3.5 Photocycloadditions 181 7.4 Carbonyl Compounds 182 7.4.1 Introduction 182 7.4.2 Photochemical Primary Processes 183 7.5 Photochemistry of Other Organic Compounds 185 7.5.1 Nitrogen Compounds 185 7.5.1.1 Overview 185 7.5.1.2 Photoisomerization of Azocompounds 186 7.5.2 Saturated Oxygen and Sulfur Compounds 186 7.5.3 Halogen Compounds 187 References 189 8 Photochemistry and Photophysics of Metal Complexes 191 8.1 Metal Complexes 191 8.2 Photophysical Properties 191 8.3 Photochemical Reactivity 192 8.4 Relationships between Electrochemistry and Photochemistry 194 8.4.1 Cobalt (III) Complexes 195 8.4.2 Copper (I) Complexes 196 8.4.3 Ru(II) Polypyridine Complexes 196 8.4.4 Excited-State Redox Potentials 199 8.5 Luminescent Metal Complexes 201 8.5.1 Polypyridine Metal Complexes 201 8.5.2 Cyclometallated Complexes 203 8.5.2.1 Ruthenium Complexes 204 8.5.2.2 Rhodium Complexes 204 8.5.2.3 Iridium Complexes 205 8.5.2.4 Platinum Complexes 207 8.5.2.5 Orbital Nature of the Emitting Excited State 212 8.5.3 Porphyrin Complexes 213 8.5.4 Chromium (III) Complexes 216 8.5.5 Lanthanoid Complexes 219 8.6 Photochemical Processes 223 8.6.1 Types of Photoreactions 223 8.6.1.1 Photodissociation and Related Reactions 223 8.6.1.2 Photooxidation?Reduction Reactions 224 8.6.1.3 Intramolecular Rearrangements 225 References 226 9 Interconversion of Light and Chemical Energy by Bimolecular Redox Processes 231 9.1 Light as a Reactant 231 9.2 Light as a Product 232 9.3 Conversion of Light into Chemical Energy 233 9.4 Chemiluminescence 235 9.5 Electrochemiluminescence 235 9.6 Light Absorption Sensitizers 237 9.7 Light Emission Sensitizers 240 References 242 10 Light-Powered Molecular Devices and Machines 245 10.1 Molecules, Self-Organization, and Covalent Synthetic Design 245 10.2 Light Inputs and Outputs: Reading, Writing, and Erasing 246 10.3 Molecular Devices for Information Processing 247 10.3.1 Photochromic Systems as Molecular Memories 247 10.3.2 Molecular Logics 249 10.3.2.1 Luminescent Sensors as Simple Logic Gates 250 10.3.2.2 AND Logic Gate 251 10.3.2.3 XOR Logic Gate with an Intrinsic Threshold Mechanism 251 10.3.2.4 Encoding and Decoding 253 10.4 Molecular Devices Based on Energy Transfer 255 10.4.1 Wires 255 10.4.2 Switches 257 10.4.3 Plug/Socket Systems 258 10.4.4 Light-Harvesting Antennas 259 10.5 Molecular Devices Based on Electron Transfer 260 10.5.1 Wires 260 10.5.2 Switches 263 10.5.3 Extension Cables 265 10.6 Light-Powered Molecular Machines 268 10.6.1 Basic Remarks 268 10.6.2 The Role of Light 268 10.6.3 Rotary Motors Based on cis?trans Photoisomerization 269 10.6.4 Linear Motions: Molecular Shuttles and Related Systems 271 10.6.5 Photocontrolled Valves, Boxes, and Related Systems 275 References 276 11 Natural and Artificial Photosynthesis 281 11.1 Energy for Spaceship Earth 281 11.2 Natural Photosynthesis 284 11.2.1 Light Harvesting: Absorption and Energy Transfer 285 11.2.2 Photoinduced Electron Transfer Leading to Charge Separation 285 11.2.2.1 Bacterial Photosynthesis 285 11.2.2.2 Green Plants Photosynthesis: Photosystem II 287 11.2.3 Efficiency of Photosynthesis 288 11.3 Artificial Photosynthesis 290 11.3.1 Artificial Antenna 293 11.3.2 Artificial Reaction Centers 296 11.3.3 Coupling Artificial Antenna and Reaction Center 299 11.3.4 Coupling One-Photon Charge Separation with Multielectron Water Splitting 301 11.4 Water Splitting by Semiconductor Photocatalysis 302 References 304 12 Experimental Techniques 309 12.1 Apparatus 309 12.1.1 Light Sources 309 12.1.2 Monochromators, Filters, and Solvents 317 12.1.3 Cells and Irradiation Equipment 319 12.1.4 Detectors 321 12.2 Steady-State Absorption and Emission Spectroscopy 323 12.2.1 Absorption Spectroscopy 323 12.2.1.1 Instrumentation 324 12.2.1.2 Qualitative and Quantitative Applications 325 12.2.1.3 Sample Measurement 325 12.2.2 Emission Spectroscopy 326 12.2.2.1 Instrumentation 326 12.2.2.2 Emission Spectra 328 12.2.2.3 Excitation Spectra 329 12.2.2.4 Presence of Spurious Bands 330 12.2.2.5 Quantitative Relationship between Luminescence Intensity and Concentration 331 12.2.2.6 Stern?Volmer Luminescence Quenching 332 12.2.2.7 Emission Quantum Yields 333 12.3 Time-Resolved Absorption and Emission Spectroscopy 335 12.3.1 Transient Absorption Spectroscopy 335 12.3.1.1 Transient Absorption with Nanosecond Resolution 335 12.3.1.2 Transient Absorption with Femtosecond Resolution 337 12.3.2 Emission Lifetime Measurements 338 12.3.2.1 Single Flash 338 12.3.2.2 Gated Sampling 339 12.3.2.3 Upconversion Techniques 339 12.3.2.4 Single-Photon Counting 341 12.3.2.5 Data Analysis 342 12.3.2.6 Phase Shift 343 12.3.2.7 Luminescence Lifetime Standards 345 12.4 Absorption and Emission Measurements with Polarized Light 346 12.4.1 Linear Dichroism 346 12.4.2 Luminescence Anisotropy 347 12.5 Reaction Quantum Yields and Actinometry 349 12.5.1 Reaction Quantum Yields 349 12.5.2 Actinometry 350 12.5.2.1 Potassium Ferrioxalate 351 12.5.2.2 Potassium Reineckate 352 12.5.2.3 Azobenzene 353 12.6 Other Techniques 353 12.6.1 Photothermal Methods 353 12.6.1.1 Photoacoustic Spectroscopy 354 12.6.1.2 Photorefractive Spectroscopy 355 12.6.2 Single-Molecule Spectroscopy 357 12.6.3 Fluorescence Correlation Spectroscopy 358 12.6.4 X-ray Techniques 360 References 361 13 Light Control of Biologically Relevant Processes 365 13.1 Introduction 365 13.2 Vision 365 13.2.1 Basic Principle 365 13.2.2 Primary Photochemical Events 367 13.3 Light, Skin, and Sunscreens 367 13.4 Photochemical Damage in Living Systems 369 13.4.1 Photochemical Damage to DNA 369 13.4.2 Photochemical Damage to Proteins 369 13.5 Therapeutic Strategies Using Light 370 13.5.1 Phototherapy 370 13.5.2 Photochemotherapy of Psoriasis 370 13.5.3 Photodynamic Therapy 371 13.5.4 Photocontrolled Delivery 373 13.6 Photocatalysis in Environmental Protection 375 13.6.1 Principles 375 13.6.2 Solar Disinfection (SODIS) 375 13.6.3 Photoassisted Fenton Reaction 376 13.6.4 Heterogeneous Photocatalysis 376 13.7 DNA Photocleavage and Charge Transport 377 13.7.1 Photocleaving Agents of Nucleic Acid 377 13.7.2 Photoinduced Electron-Transfer Processes in DNA 378 13.8 Fluorescence 379 13.9 Bioluminescence 379 References 380 14 Technological Applications of Photochemistry and Photophysics 385 14.1 Introduction 385 14.2 Photochromism 385 14.3 Luminescent Sensors 388 14.3.1 Principles 388 14.3.2 Amplifying Signal 389 14.3.3 Wind Tunnel Research 389 14.3.4 Thermometers 391 14.3.5 Measuring Blood Analytes 393 14.3.6 Detecting Warfare Chemical Agents 395 14.3.7 Detecting Explosives 397 14.4 Optical Brightening Agents 399 14.5 Atmospheric Photochemistry 400 14.5.1 Natural Processes Involving Oxygen 400 14.5.2 Ozone Hole 401 14.6 Solar Cells 402 14.6.1 Inorganic Photovoltaic (PV) Cells 402 14.6.2 Organic Solar Cells (OSCs) 403 14.6.3 Dye-Sensitized Solar Cells (DSSCs) 405 14.7 Electroluminescent Materials 407 14.7.1 Light-Emitting Diodes (LEDs) 407 14.7.2 Organic Light-Emitting Diodes (OLEDs) 407 14.7.3 Light-Emitting Electrochemical Cells (LECs) 409 14.8 Polymers and Light 411 14.8.1 Photopolymerization 411 14.8.2 Photodegradation 411 14.8.3 Stabilization of Commercial Polymers 412 14.8.4 Photochemical Curing 413 14.8.5 Other Light-Induced Processes 413 14.8.6 Photolithography 414 14.8.7 Stereolithography 415 14.8.8 Holography 416 14.9 Light for Chemical Synthesis 417 14.9.1 Photochlorination of Polymers 418 14.9.2 Synthesis of Caprolactam 418 14.9.3 Synthesis of Vitamins 418 14.9.4 Perfumes 419 References 420 15 Green (Photo)Chemistry 425 15.1 Definition, Origins, and Motivations 425 15.2 Photochemistry for Green Chemical Synthesis 426 15.3 Photocatalysis 428 15.3.1 Heterogeneous Photocatalysis 428 15.3.2 Homogeneous Photocatalysis 429 15.4 Photocatalysis in Synthesis 429 15.4.1 Alkanes 430 15.4.2 Alkenes 430 15.4.3 Alkynes 432 15.4.4 Sulfides 432 15.5 Photocatalytic Pollution Remediation 433 15.6 Use of Solar Energy in Green Synthesis 434 References 436 16 Research Frontiers 439 16.1 Introduction 439 16.2 Aggregation-Induced Emission 439 16.3 Phosphorescence from Purely Organic Materials by Crystal Design 441 16.4 Synthesis of a 2D Polymer 443 16.5 Photocontrolled Relative Unidirectional Transit of a Nonsymmetric Molecular Wire through a Molecular Ring 444 16.6 Molecular Rotary Motors Powered by Visible Light via Energy Transfer 445 16.7 Cooperation and Interference in Multifunction Compounds 447 16.8 Singlet Fission 449 16.9 One-Color Photochromic System 452 16.10 Photonic Modulation of Electron Transfer with Switchable Phase Inversion 454 16.11 Dye-Sensitized Photoelectrosynthesis Cells (DSPECs) 457 References 459 Index 463

About the Author

Vincenzo Balzani is Emeritus Professor of Chemistry at the University of Bologna, Italy. His scientific activity is documented by six books and more than 550 papers in the fields of photochemistry, supramolecular chemistry, molecular machines, and solar energy conversion. His overall h-index is 87. The high international reputation of his studies and the appreciation for his innovative work is testified by various awards and the great number of invitations (more than 300) to present lectures and seminars all over the world.Paola Ceroni is an Associate Professor at the University of Bologna. In 1998 she obtained her PhD degree in Chemical Sciences at the University of Bologna, after a period in the United States (Prof. Allen J. Bard's laboratory). Her PhD thesis was awarded by the Semerano prize from the Italian Chemical Society. Current research is focused on photochemistry and electrochemistry of molecular and supramolecular systems with particular emphasis towards photoactive dendrimers and nanomaterials. She is co-author of about 140 scientific papers. She is the principal investigator of an ERC Starting Grant for the development of hybrid materials for solar energy conversion. Alberto Juris is former Associate Professor of General and Inorganic Chemistry at the University of Bologna. His research activity focused on photochemistry and photophysics of mono- and polynuclear transition metal compounds, including those with dendritic structure, solar energy conversion processes, and luminescent sensors. He is co-author of about 100 papers. Among these, a review article published in 1988 on Ru(II) polypyridine complexes has been cited in the scientific literature more than 3000 times.

Reviews

This is a very timely book that provides an up to datepresentation of photochemistry and photophysics in which the twosubject areas are clearly interrelated. (ChemistryWorld, 14 October 2014)

EAN: 9783527334797
ISBN: 3527334793
Publisher: Wiley-VCH Verlag GmbH
Dimensions: 24 x 17 x 2.5 centimetres (1.09 kg)
Age Range: 15+ years
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