Biomimetic and bioinspired systems
(Cont.)
light absorption and sensitization,
239 – 251
metalloenzyme catalysts, 238
origins and impacts, 237f
photochemical modeling
bioactive molecules release,
275 – 276
charge separation, 269– 270
hydrogen atom transfer, 274
oxygen activation, 270– 274
photochemical reactivity
electrons, 252– 254
protons, 254– 255
spin, 255– 256
selectivity and regulation
catalytic activity controlling,
258 – 259
controlling reaction pathways,
257 – 258
Born–Oppenheimer approximation,
204 – 205
C
Carbonate photoreduction, 354– 360
Carbon dioxide docking sites,
264 – 265
Carbon dioxide (CO 2 ) photosplitting
artificial photosynthesis, 353
CuI(CO 3 )CuI(prophos), 354– 357
natural photosynthesis, 353
scheme, 354
Catalysis, 397, 398f
Catecholamines (CAs), 22
4-Chlorophenol (4-CP), 378– 379
11-cis-retinal, 240f
Cocatalyst loading, 419– 420
Covalently linked donor–acceptor
system, 260f
Cytochromec, 241
D
Dendrimers
bis-cyclam core, 126f
classification, 108
definition, 106– 108
depolarization, 129
energy level diagram, 132f
functions, 106– 107
initial development, 106
intrinsic photochemical and
photophysical properties
deactivation, 108– 109
Dexter-type mechanism, 111
excimers and exciplexes, 112
excited state quenching, 111
Förster-type mechanism, 111
generic molecule, 109f
lifetime of an excited state, 110
quantum yields, 110– 111
sensitization process, 110– 111
limiting structures, 124– 125
metal complex as core
dendrimer 1^2 þ, 113
[Ru(bpy) 3 ]^2 þ core, 114f
metal complexes as branching
centers
decanuclear Ru^2 þ metal complex,
116f
heterometallic species, 117
polytopic-chelating ligands, 115
multiple coordination sites
amide coordinating units, 118– 120
amine coordinating units, 120– 122
naphthalene-like chromophores,
125
role, 132– 133
scaffolds, 107
schematic representation, 106f
self-assembly, 131– 132
single coordinating site
acetonitrile–dichloromethane, 123
cyclam, 123
exciplex formation, 123– 124
three-component system, 130– 131
titration profiles, 127– 129
Dendritic ligands.SeeDendrimers
Dinitrogen splitting
lack of reactivity, 360– 361
(-N 2 )[Mo(N[tert-Bu]Ar) 3 ] 2 , 361
[(NH 3 ) 5 OsII(-N 2 )OsIII(NH 3 ) 5 ]^5 þ,
361 – 366
d^6 metal complexes
aggregation-induced emission
enhancement, crystals
crystallization process, 72– 73
organometallic species, 71– 72432 INDEX