Photochemistry_of_Organic

Index

Mechanistic probe, 284 Meisenheimer complex, 289 Melanin, 410

Membrane

of cell, 408 Mercury arc

high-pressure, 74 low-pressure, 73 medium-pressure, 73

Merrilactone A, 304

Merry-go-round, 129 Meta effect, 333 Metalloenzyme, 428 Metalloporphyrin, 379

Metal-to-ligand charge transfer, 337 Metal-to-metal charge transfer, 337 Methacrylate, 436

Methoxybenzyl acetate, 333 Methyl iodide, 396

Methyl viologen, 451 Methylcyclohexene, 253

Methylene Blue, 395, 408, 413, 420 Micelle, 308

Microchannel plate, 81 Microwave discharge, 409 Mineralization, 441 Mirror-image relationship, 42, 86 Mixed-valence compounds, 188

Molar absorption coefÞcient, 30, 32, 35, 86, 115, 231

Molecular ruler, 51, 53 Mulliken symbols, 149 Multiplicity, 15, 17, 26, 46 Mutagenesis, 265

N,N-dimethylaniline, 371 Nanofabrication, 437 Nanomachine, 376 Nanotechnology, 282, 348, 364, 375 2-Naphthaldehyde, 303

Naphthalene, 25, 58, 89, 154, 155, 166, 169, 179, 184, 226

Naphthalene-1,2-dicarboxylic, anhydride, 335

2-Naphthol, 194 Naphthoquinone, 39, 294, 327

1,2- and 1,4-, 329

1,4-, 330 methide, 175

Naphthyl acetate, 336

557

N-bromosuccinimide, 393 NBS, 393

Necrosis, 411

NEER principle, 223, 235, 244 Negative image generation, 437 Neonatal jaundice, 237 Neuron, 334

Neurotransmitter, 364 Nitrene, 355, 357 Nitric oxide, 359 Nitrile, 371

ylide, 199, 351 Nitrite ester, 359 Nitroalkane, 362 4-Nitroanisole, 291 Nitroarene, 362 Nitrobenzene, 340, 362

o-Nitrobenzyl derivative, 363 o-Nitrobenzyl group, 365 Nitrogen

compound, 340 elimination, 344, 355, 360 oxide, 407

Nitrone, 359 2-Nitrosoacetophenone, 365 Nitrostyrene, 253 2-Nitrotoluene, 363 Nitroveratryl group, 368 N-methylaniline, 371

N-methyl-N-(trimethylsilylmethyl)- benzenamine, 372

Nonadiabatic reactions, 69 Non-alternant hydrocarbon (NAH), 156 Nonconcerted mechanism, 256 Noncrossing rule, 69

Nonlinear optics, 78

Non-steroidal anti-inßammatory drug (NSAID), 331

Norbornadiene, 328

Norbornanone, 302 Norbornyl halide, 396

Normalization of wavefunctions, 18 Norrish

type I reaction, 204, 215, 305

type II reaction, 177, 215, 219, 311 cleavage/cyclization ratio, 313

Novolak, 438

N-oxide, 359 Nucleophile, 289 Nylon-6, 394

O-atom attack, Paterno`ÐB€uchi reaction, 302 OccamÕs razor, 102, 184

Occupation number, 143 Ocean, 411 Octahedrane, 286 Octamethylcubane, 298 Oct-2-ene, 231 Octanethiol linker, 375 Oligosaccharide, 366 One-bond twist, 235 Operator, 13, 20

dipole moment, 20 Hamiltonian, 13 perturbation, 23

Ophthalmic lense, 346 Optical data storage, 246

Optical information storage, 348 Optical switch, 348

Orbital

angular momentum, 16 atomic (AO), 13

highest occupied MO (HOMO), 152 H€uckel molecular (HMO), 140

linear combination of AOs (LCAO), 21, 138 lowest unoccupied MO (LUMO), 152 molecular (MO), 138

nonbonding (NBMO), 142 symmetry rules, 241, 256 virtual, 161

Organic crystal, 309 photochemistry, 259, 315

Organoiodine(III) compound, 402 Orthonormal, 21, 34, 105, 140 Oscillator strength, 35, 86 Oxa[3.3.3]propellane, 304 Oxacarbene intermediate, 309 Oxadiazole, 360

Oxa-di-p-methane rearrangement, 250 Oxazirine, 359

Oxetane, 263, 300, 327 Oxidation processes, 443 Oxidative addition, 337 Oxime, 343, 350 Oxygen, 240, 404, 496

compounds, 293 evolving complex, 428 excited, 408

pressure method, 89 production, 428 quenching, 82, 89

Oxygenation, 404

Ozone, 406, 409

depletion, 407

hole, 407

layer, 265

Ozonide, 409

Paclitaxel, 269 Paint, 439 Paracyclophane, 286

Parallel approach, Paterno`ÐB€uchi reaction, 301 Parity-forbidden transitions, 169 Paterno`ÐB€uchi reaction, 240, 265, 300, 385 Pauli principle, 15, 19, 139, 152, 207

PBDE, 399

PCB, 399

PCDD, 399

PDT, 410 Penta-1,3-diene, 242

See pentadiene: 1,3-Pentadiene 1,3-, 242, 419

Perepoxide, 412, 419 Perfume, 395 Pericyclic reaction, 241

Peroxyacyl nitrate (PAN), 407 Peroxyoxalate chemiluminescence, 224 Perpendicular approach, Paterno`ÐB€uchi

reaction, 301 Perrin diagram, 25 Perturbation

operator, 36, 33, 47 theory, 22, 36, 137, 144

Þrst-order, 144

degenerate orbitals, 146, 150 second-order, 145

PES, 67

pH study, 365 Phenacyl

2,5-dimethyl, 326

2-methyl, 325 ester, 371

Phenanthrene, 245 Phenanthrenequinone, 9,10-, 329 Phenol, 289

Phenyl acetate, 335

benzoate, 332 Phenylacetic acid ester, 333 Phenylazirine, 352 Phenylbenzophenone, 4-, 301

Photoregulation of protein, 364 Photoreleasable group, 364 Photoremovable

group, 387

protecting group, 216, 326, 334 Photoresist, 437

Photo-ring contraction, 278 Photosantonic acid, 272 Photoselection, 92 Photosensitivity, 409

Photosensitization, 237, 250, 253, 263, 273, 348, 372, 408, 424

Photosensitized polymerization, 374 Photosensitizer, 374, 379, 408, 410, 423, 446

optically active, 239 Photo-Smiles rearrangement, 370

Photostationary state, 117, 231, 233, 238, 242, 246, 277, 325, 343, 346

Photosubstitution, 288

nucleophilic, 287, 291, 370, 396, 401 Photoswitching, 348

Photosynthesis, 3, 427

Photosystem I, II, 428

Phototherapy, 237, 266

Phototoxicity, 331, 409

Phototransduction, 236 Phototransposition, 276, 360 Photovoltaic cell, 444, 446

Photo-Wolff rearrangement, 353, 400, 438 pHÐrate proÞles, 220

Phthalimide, 321 Phthalocyanine, 448 Phytoplankton, 412 Pinacol, 298, 299 Piperylene, 124 Platt

perimeter model, 168 symbol, 93

PMO theory, 158 Point group, 148 Pollutant

anthropogenic, 395, 407, 451 organic, 441

persistent environmental, 399

Poly(vinyl cinnamate), 439 Polybrominated diphenyl ether, 399 Polycarbonate, 348

Polycyclic aromatic hydrocarbon, 281, 346 Polyethylene, 314

Polyhaloalkane, 397 Polymer, 314, 374, 395 Polymethacrylate, 439

Poly(phenyl vinyl ketone), 314 Polypyridyl complex, 447 Polypyrrole, 374

Polystyrene, 314, 366 Population inversion, 31, 77 Porphyria, 410

Porphyrin, 341, 379, 410, 431 Positive image generation, 437 Potential energy surface (PES), 14,

67, 223 Prebiotic chemistry, 265 Prefulvene, 276 Previtamin D, 235, 243 Primary

photochemical process, 28 photoproduct, 28

Primitive atmosphere, 361 Principal component analysis, 103 Print-out effect, 448

Prismane, 277 Progesterone, 392 Propan-2-ol, 267, 298, 362 Propenylanisole, 414 Propenylbenzene, 449 Protein, 357, 427

folding, 53, 54, 134 phosphatase inhibitor of, 416

Proton pump, 428

transfer, 192, 436 Protoporphyrin IX, 410 Provitamin D, 243, 394

Pseudo quantum yield, 116, 117 Psoralen, 266, 409

Psoriasis, 266

P-type delayed ßuorescence, 63 PumpÐprobe spectroscopy, 99 Purple bacteria, 427

Pyrazole, 360

Pyrene, 40, 60, 61, 62, 64, 93 Pyridazine, 340

Pyridine, 278, 281, 340 Pyridinium salt, 278

Pyrimidine, 265

Pyrrole, 374, 379

Pyrylium cation, 278

efÞciency, 45 yield, 39, 110, 231

pseudo, 116 Quartet state, 205 Quenching, 121, 384

concentration, 56, 126 static, 126

Quinone, 327, 329, 346, 427

RabbitÕs ears, 293 Radiant

intensity, 49 power, 112

Radiationless transition, 26, 35

Radiative lifetime, 121 transition, 26

Radical

chain mechanism, 391 clock, 284, 320 phenyl, 326, 451 reaction, 351 stability, 343

Radical ion, 255, 434 Rate

constant, 119 law:

Þrst-order, 99 second-order, 99

rate-determining step, 196 Rayleigh scattering, 12 Rayonet reactor, 255 Reaction

centre, 427 mechanism, 183

Ring expansion, 356 Rose Bengal, 127, 408 Rose oxide, 395

Rule of Þve, 270 Ruthenium(II) (phenanthroline)-

dipyridophenazine complex, 377 Rydberg state, 231, 252

Santonin, 272, 334 Saturation, 12 Scandine, 283

Schenck mechanism, 240, 419, 433 Sch€onßies symbol, 148

Secondary photoreactions, 110 Secular

determinant, 22, 140, 160 equation, 21, 140, 160

Selection rule, 34 Self-consistent Þeld, 161 Self-modelling, 108 Self-quenching, 123 Semibullvalene, 248 Semiconductor, 430, 442, 446

Sensitization, 57, 125, see energy transfer by organic dye, 444

Sigmatropic photorearrangement, 246, 272, 336, 341

Signal transduction cascade, 236 Signalling pathway, 358 Silicon, 446

Silver halide, 447

562

Silyl compound, 262 Single-molecule spectroscopy, 133

Single-crystal-to-single-crystal reaction, 261 Singlet

oxygen, 47, 65, 266, 408, 419 microscopy, 411

state, 17 covalent, 207

energy transfer, 57

Singular value decomposition, 103 Skell hypothesis, 199

Skin, 244, 409 cancer, 265, 267

photosensitivity, 331 Slater determinant, 139, 160 Small-ring compound, 309 SN1*, 396, 401

SN1Ar*, 288

SN2Ar*, 291, 370, 401 Snow, 411

Solar constant, 2

energy conversion, 430 energy storage, 4 radiation, 3, 74, 265, 375 simulator, 85

UV radiation, 411 Solid-state

photochemistry, 315

Solvent shifts (UV spectra), 294 Soret band, 341

Specks of silver, 448 Spectral

bandpass, 90

overlap integral, 49, 51 radiant

intensity, 49 power, 29, 90, 111

Spectroscopic minima, 67 Spin

centre shift, 320

spin angular momentum, 16 spin function, 18

spinÐorbit coupling, 18, 36, 38, 172, 213 spin-statistical factor, 47

Spirooxazine, 346

Spiropyran, 346

Squaraine, 448

SR+ N1Ar*, 289

SRÐ N1Ar*, 289

Index

Standard electrode potential, 369 Steady-state approximation, 45, 120 StepÐscan FTIR, 110

Stepurane, 247 Stereochemistry, 260

StereospeciÞc reaction, 241, 256 StereospeciÞty, 256 SternÐVolmer equation, 122

curvature, 123, 126

Stilbene, 227, 232, 233, 245, 255, 345 Stimulated emission, 30

Stokes shift, 28, 43 StokesÐEinstein equation, 45 Streak camera, 81, 91 StricklerÐBerg relation, 32 Styrene, 255, 414 Styrylamine, 255 Styrylpyrylium trißate, 261 Sulfenate ester, 388 Sulfonate, 386

aryl, 287 Sulfone, 386

aliphatic, 386 aromatic, 386

Sulfoxide, 388

Sulfur compounds, 381 Supercritical solvent, 335 Superexchange mechanism, 192 Superoxide anion, 406 Suprafacial approach, 246, 256

Supramolecular chemistry, 233, 348 Surface photochemistry, 375 Surface water, 411

Symmetry operation, 148 Symmetry-adapted lone pair, 293 Symmetry-forbidden transitions, 153 Synthesis

organic, 364

Tachysterol, 235

Target factor transformation, 105, 108 Taxol, 269

Teßon porphyrin, 379 Template-induced enantioselective

photoreaction, 239 Tetracycline, 409 Tetrahydroxyphenyl chlorin, 410

Tetramethylcyclobutanone, 2,2,4,4-, 309 Tetramethylethene, 252 Tetraphenylporphyrin, 408, 414, 417

Index

Tetrapyrrole, 341 Tetrazole, 360 Thiobenzaldehyde, 383

Thiobenzophenone, 383, 385 Thiocarbonyl compound, 382, 383 Thione, 383

alkyl aryl, 384 Thiophenol, 381 Thiourea, 381 Thioxanthone, 381, 434

Through-bond interaction, 214 Through-space interaction, 214 Thymine, 266

Titanium dioxide, 442, 450 modiÞed, 444, 451

Titanium isopropoxide, 443 Toluene, 238 Toluenesulfonate, 387 Transition

metal, 257

complex, 337, 374

heterogeneous photocatalysis, 442 homogeneous photocatalysis, 440

radiationless, 35 Transition moment, 33 Transmittance, 40 Trapping agent, 323 Triad, 367, 431 Triazole, 360 Tributylstannane, 298 Triene, 242, 243 Triplet state, 17

sensitizer, 231

triplet energy transfer, 54 triplet excimer, 63 triplet sensitization, 125

tripletÐtriplet annihilation, 40, 47, 64, 96 Tris(2,20 -bipyridine)ruthenium(II) ion, 379 Tris(4-methylphenyl)octaßuoroporphyrin, 379 Tunnelling, 384

effect, 308 Twist

of bond, 305 Two-level emission, 40

Two-photon excitation, 365

Uncertainty principle. See Heisenberg Uniform reaction, 104, 114

Unit

SI base, 6

563

UV curing, 395, 438

UV nanoimprint lithography, 439

UV stabilizer, 315

UVA, UVB, UVC radiation, 3

Vacuum UV, 231 Valence band, 442 Valerophenone, 313 Variation theorem, 21 Vavilov rule, 40, 382 Vector, 15, 103 Vertical transition, 41 Vibrational

borrowing, 42

redistribution (IVR), 28, 36, 68 relaxation, 28, 36, 48

Vibronic transition, 27, 31, 34 Vision, 11, 236

Vitamin

A, 236, 394

D, 235, 243

Volatile organic compounds (VOCs), 407

Water splitting, 430 Wavefunction, 13

complex, 45 symmetry, 148, 153

Waveguided illumination, 348 Wavenumber, 86

WoodwardÐHoffmann rules, 177, 224, 241, 246, 256

Xanthone, 58, 64

Xerography, 448

Xylene, 238, 253, 277

Yang cyclization, 311, 317, 323

Ylide, 351, 352

Ynamine, 219

Ynol, 219

Zeolite, 239, 421 Zimmerman reaction, 248 Zinc porphyrin, 432

Zinc sulÞde, 458

Zinc tetrakis(perßuorophenyl)porphyrin, 341

Zinc tetraphenylporphyrin, 348 Zwitterion, 207, 272, 280, 300, 413