Introduction .................................................. vii
I Spectroscopies on paramagnetic substances .................... 1
1 Electronic spectroscopies with lanthanides ................... 3
1.1 Electronic states of lanthanides ........................ 3
1.1.1 General scheme ................................... 3
1.1.2 The free ions .................................... 4
1.1.3 Crystal field hamiltonian ........................ 5
1.2 ƒƒ transitions .......................................... 9
1.2.1 Transition dipoie moments and rotational
strengths ........................................ 9
1.2.2 Magnetic dipoie transition moments .............. 10
1.2.3 Electric dipoie transition moments .............. 11
1.2.4 Selection rules and class of transitions ........ 13
1.3 Choice of the lanthanide ion ........................... 16
1.4 Symmetric crystal fields ............................... 19
1.4.1 Symmetry of the crystal field ................... 19
1.4.2 Selection rules based on symmetry ............... 20
1.4.3 Yb3+ in a trigonal or tetragonal crystal
field ........................................... 21
Bibliography ................................................ 23
2 NMR of paramagnetic molecules ............................... 25
2.1 Hyperfine shift ........................................ 25
2.1.1 Fermi contact coupling .......................... 25
2.1.2 Dipolar coupling ................................ 28
2.1.3 Bleaney's theory ................................ 29
2.1.4 Separation of contact and pseudocontact
contributions ................................... 33
2.2 Relaxation ............................................. 35
2.2.1 S-mechanism ..................................... 35
2.2.2 Curie or χ-mechanism ............................ 38
2.2.3 Relative relevance of the different
contributions ................................... 40
2.3 Choice of the lanthanide ion ........................... 42
Bibliography ................................................ 13
II Inert lanthanide chelates .................................. 47
3 С4 symmetric complexes ...................................... 49
3.1 Generalities on the DOTA-like systems .................. 49
3.2 Chiral analogues ....................................... 52
3.2.1 YbDOTMA ......................................... 53
3.2.2 YbDOPEA and YbDONEA ............................. 53
3.2.3 YbDOTAM-Phe, YbDOTAM-Ile and YbDOTAM-Pro ........ 56
3.2.4 YbTHP ........................................... 56
3.3 Description of the method .............................. 58
3.4 NMR analysis: description of the coordination cage ..... 60
3.4.1 YbDOTMA ......................................... 60
3.4.2 YbDOPEA and YbDONEA ............................. 71
3.4.3 YbDOTAM-Phe. YbDOTAM-Ile and YbDOTAM-Pro ........ 77
3.4.4 YbTHP ........................................... 77
3.4.5 [YbTHP]2 ........................................ 82
3.5 NIR-CD analysis: chirality of the coordination cage .... 89
3.5.1 YbDOTMA ......................................... 89
3.5.2 YbDOPEA and YbDONEA ............................. 96
3.5.3 YbDOTAM-Phe. YbDOTAM-Ile and YbDOTAM-Pro ........ 98
3.5.4 YbTHP ........................................... 99
3.6 Axial dynamics ........................................ 104
3.6.1 YbDOPEA and YbDONEA ............................ 104
3.6.2 YbTHP .......................................... 112
3.7 Generalization to the whole lanthanide transition ..... 114
3.8 Conclusions ........................................... 119
Bibliography ............................................... 123
4 CD spectra calculations on YbDOTMA ......................... 129
4.1 Parameters employed ................................... 130
4.2 Free-ion wave functions ............................... 130
4.3 Crystal field parameters and transition frequencies ... 132
4.4 Dipole and rotatory strengths ......................... 133
4.5 Discussion ............................................ 135
4.6 Conclusions ........................................... 136
Bibliography ............................................... 136
5 Lanthanide complexes as catalysts .......................... 139
5.1 Heterobimetallic Ln M3BINOL3 complexes ................ 139
5.2 Crystal structure of Yb Na3BINOL3 ..................... 142
5.3 NMR data collection on YbNa3BINOL3 .................... 143
5.3.1 Structural optimization ........................ 145
5.4 UV absorption and CD spectra .......................... 148
5.4.1 Effect of the alkaline ion: data on
YbK3BINOL3 ..................................... 150
5.5 NIR absorption and CD spectra ......................... 152
5.6 Conclusions ........................................... 153
Bibliography ............................................... 154
III Labile lanthanide adducts ................................. 157
6 Spectroscopic determination of the configuration of
chiral diols ............................................... 159
6.1 The lanthanide diketonate method ...................... 160
6.1.1 Generalities ................................... 160
6.1.2 A survey of the diketonates method and its
extention to the NIR ........................... 161
6.1.3 UV-СD spectra of mixtures of chiral diols and
Yb(fod)3 ....................................... 163
6.1.4 NIR-CD spectroscopy ............................ 164
6.1.5 NMR of 1:1 mixtures of diols and Yb(fod)3 ...... 164
6.1.6 Variable molar ratio data ...................... 166
6.1.7 Analysis of the NMR pseudocontact shifts ....... 169
6.1.8 Structure and dynamics of the chiral species ... 171
6.2 Discussion ............................................ 172
6.3 A new method with Yb Inflate .......................... 173
6.1 Conclusions ........................................... 176
Bibliography ............................................... 177
7 Lanthanides as substitutes for "silent" metal ions ......... 181
7.1 Yb3+ complexes with anthracycline antitumor
antibiotics ........................................... 181
7.2 Dimerization constant and structure of 26 in
solution .............................................. 183
7.3 Stoichiometry of Yb-26 complexes ...................... 185
7.4 Metal ion binding site of 26 .......................... 190
7.5 Detection of second complex Yb-26 ..................... 193
7.6 Conclusions ........................................... 195
Bibliography ............................................... 196
8 Interaction of YbDOTA with γ-cyclodextrin .................. 199
8.1 Protein-bound contrast agents ......................... 199
8.2 Cyclodextrins and lanthanide complexes ................ 200
8.3 NIR-CD of YbDOTA with γ-CD ............................ 201
8.4 Conclusions ........................................... 203
Bibliography ............................................... 203
Conclusions ................................................... 205
IV Appendix .................................................. 207
A Experimental ............................................... 209
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