Pintacuda G. NMR and NIR-CD studies on lanthanide complexes in solution: tesi di perfezionamento. - Pisa: Scuola Normale Superiore, 2004. - xii, 223 p.: ill. - Bibliogr. at the end of the chapters. - ISBN 88-7642-143-2  Место хранения:   032 | Институт органической химии им. Н.Н.Ворожцова СО РАН | Новосибирск | Библиотека

Оглавление / Contents

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