Photochemistry and Photophysics of Coordination Compounds

More documents

Recommendations

Info

Photochemistry and Photophysics of Coordination Compounds: Copper 91 Fig. 21 Temperature dependence of the luminescence spectra of [Cu(7)2] + (top) and [Cu(8)2] + (bottom) in CH2Cl2 MeOH 1:1 (v/v). In the fluid domain (up to 170 K) emission intensity decrease and spectral red-shifting is observed by lowering temperature in both cases. By contrast when the solvent matrix becomes rigid (around 120 K), the two compounds behave differently. For the 2,9-dialkylphenanthroline complex (bottom panel) a complete reversal of the previous trend is observed with intensity recovery and blue shift. At 96 K a very strong luminescence band is recorded
92 N. Armaroli et al. Fig. 22 Ligand 12, 2-(3,5-di-tert-butyl-4-methoxyphenyl)-9-(2,4,6-trimethylphenyl)-1,10phenanthroline (Fig. 22). This finding gives further support to the notion that steric factors are by far more important than electronic factors. The room temperature lifetime of [Cu(12)2] + in oxygen free solution (285 ns) is scarcely affected under air-equilibrated conditions (266 ns) and is remarkably high also in CH3OH (182 ns), a solvent where most [Cu(NN)2] + do not show any luminescence. This rather unusual solvent insensitivity of the lifetime is observed also for [Cu(5)2] + (Fig. 14) suggesting that tert-butyl groups are very effective in preventing the formation of the pentacoordinated exciplex at room temperature [74]. On the other hand, in striking contrast with [Cu(12)2] + , [Cu(5)2] + is virtually non-luminescent in 77 K rigid matrix, highlighting once again the subtle factors affecting the molecular structure and, accordingly, the emission performance. Probably, in [Cu(12)2] + ,thekey structural features causing good luminescence performance are the methyl residues on the 2 and 6 position of a phenyl substituent (Fig. 22). Solid state measurements confirm the strong dependence of the excited state lifetimes of [Cu(NN)2] + complexes on geometric distortions. In particular it has been found that there is a good linear correlation between the ξCD parameter (see Sect. 2.1, Eq. 1) and the measured lifetime both at room temperature and at 17 K: the smaller the distortion from the ideal pseudotetrahedral geometry (high ξCD parameter), the longer the lifetime [56]. 2.5 Photoinduced Processes in Multicomponent Systems Based on [Cu(NN)2] + Complexes Templated synthesis of Cu(I)-bisphenanthrolines has prompted the design and construction of sophisticated multicomponent architectures comprising one or more [Cu(NN)2] + centers in tandem with other chromophores, typ-
Page 1 and 2:
280 Topics in Current Chemistry Edi
Page 3 and 4:
Photochemistry and Photophysics of
Page 5 and 6:
Volume Editors Prof. Vincenzo Balza
Page 7 and 8:
Topics in Current Chemistry Also Av
Page 9 and 10:
X Preface nation Compounds. The ven
Page 11 and 12:
Contents Photochemistry and Photoph
Page 13 and 14:
Top Curr Chem (2007) 280: 1-36 DOI
Page 15 and 16:
Page 17 and 18:
Page 19 and 20:
Page 21 and 22:
Page 23 and 24:
Page 25 and 26:
Page 27 and 28:
Page 29 and 30:
Page 31 and 32:
Page 33 and 34:
Page 35 and 36:
Page 37 and 38:
Page 39 and 40:
Page 41 and 42:
Page 43 and 44:
Page 45 and 46:
Page 47 and 48:
Page 49 and 50:
Top Curr Chem (2007) 280: 37-67 DOI
Page 51 and 52: Photochemistry and Photophysics of
Page 81 and 82: 70 N. Armaroli et al. (e.g. catenan
Page 83 and 84: 72 N. Armaroli et al. can be classi
Page 85 and 86: 74 N. Armaroli et al. Fig. 2 Qualit
Page 87 and 88: 76 N. Armaroli et al. Fig. 3 Theblu
Page 89 and 90: 78 N. Armaroli et al. In the CuA mi
Page 91 and 92: 80 N. Armaroli et al. pseudo-rotaxa
Page 93 and 94: 82 N. Armaroli et al. Fig. 11 Relat
Page 95 and 96: 84 N. Armaroli et al. Fig. 13 Absor
Page 97 and 98: 86 N. Armaroli et al. leading to a
Page 99 and 100: 88 N. Armaroli et al. Fig. 18 Trans
Page 101: 90 N. Armaroli et al. Fig. 20 Ligan
Page 105 and 106: 94 N. Armaroli et al. tionalized de
Page 107 and 108: 96 N. Armaroli et al. Fig. 24 Absor
Page 109 and 110: 98 N. Armaroli et al. prisingly, PP
Page 111 and 112: 100 N. Armaroli et al. A different
Page 113 and 114: 102 N. Armaroli et al. Cuprous clus
Page 115 and 116: 104 N. Armaroli et al. Fig. 32 Sche
Page 117 and 118: 106 N. Armaroli et al. Fig. 34 A te
Page 119 and 120: 108 N. Armaroli et al. which are va
Page 121 and 122: 110 N. Armaroli et al. Acknowledgem
Page 123 and 124: 112 N. Armaroli et al. 58. Miller M
Page 125 and 126: 114 N. Armaroli et al. 123. Armarol
Page 127 and 128: Top Curr Chem (2007) 280: 117-214 D
Page 153 and 154:
Page 155 and 156:
Page 157 and 158:
Page 159 and 160:
Page 161 and 162:
Page 163 and 164:
Page 165 and 166:
Page 167 and 168:
Page 169 and 170:
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
Page 187 and 188:
Page 189 and 190:
Page 191 and 192:
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
Page 199 and 200:
Page 201 and 202:
Page 203 and 204:
Page 205 and 206:
Page 207 and 208:
Page 209 and 210:
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Page 221 and 222:
Page 223 and 224:
Page 225 and 226:
Top Curr Chem (2007) 280: 215-255 D
Page 227 and 228:
Page 229 and 230:
Page 231 and 232:
Page 233 and 234:
Page 235 and 236:
Page 237 and 238:
Page 239 and 240:
Page 241 and 242:
Page 243 and 244:
Page 245 and 246:
Page 247 and 248:
Page 249 and 250:
Page 251 and 252:
Page 253 and 254:
Page 255 and 256:
Page 257 and 258:
Page 259 and 260:
Page 261 and 262:
Page 263 and 264:
Page 265 and 266:
Page 267 and 268:
258 Author Index Volumes 251-280 Be
Page 269 and 270:
260 Author Index Volumes 251-280 Er
Page 271 and 272:
262 Author Index Volumes 251-280 Je
Page 273 and 274:
264 Author Index Volumes 251-280 Me
Page 275 and 276:
266 Author Index Volumes 251-280 Sa
Page 277 and 278:
268 Author Index Volumes 251-280 Vi
Page 279 and 280:
Subject Index Alkyne bridges 148 An
Page 281:
Subject Index 273 Rh(III) cyclometa
show all

Photochemistry and Photophysics of Coordination Compounds

Create successful ePaper yourself

Delete template?

Save as template?