ISBN-13: 9783527334797 / Angielski / Miękka / 2014 / 504 str.
ISBN-13: 9783527334797 / Angielski / Miękka / 2014 / 504 str.
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.
Written by an excellent author team combining scientific experience with didactical writing skills, this much–needed textbook covers the spectrum from basic concepts of photochemistry and photophysics to selected examples of current applications and research.
This is a very timely book that provides an up to date presentation of photochemistry and photophysics in which the two subject areas are clearly interrelated. (Chemistry World, 14 October 2014)
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
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.
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.
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