TítuloDiseño de quelatos de lantánidos de alta estabilidad con interés en imagen molecular

Texto completo

(1)Capítulo VIII Anexos.

(2)

(3) Espectros de RMN, Masas e Infrarrojo de los Precursores y Ligandos.

(4)

(5) Dimetilpiridina-2,6-dicarboxilato (1) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(6) DEPT-RMN (CDCl3) (/ppm). COSY-RMN (CDCl3) (/ppm).

(7) HSQC-RMN (CDCl3) (/ppm). HMBC-RMN (CDCl3) (/ppm).

(8) Espectro de masas ESI+ +TOF MS: 0.449 to 0.867 min from Sample 2 (ARR-DE en DCM/MeOH) of 2010_08580_ARR-DE_esitof01.wiff a=3.59904198893796640e-004, t0=-1.27470695516452660e+001 (Turbo Spray). Max. 2083.5 counts.. 196.06. 100% 95% 90% 85% 80% 75% 70% 65% R e l. I n t . ( % ). 60% 218.04. 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 168.06. 136.04140.07 120. 140. 160. 180. 213.09. 223.02227.02. 200. 220. 413.10 312.56. 240. 260. 280 300 m/z, Da. 320. 340. 360. 380. 400. 420. 440. 460. 480. 994.82 950.65 888.80 852.15 811.91 752.91 721.00 694.41 645.56 574.03 522.17 462.65 433.44 387.81 352.92. 1323.52 1290.35 1243.12 1196.55 1163.46 1141.68 1080.11. 1449.07 1436.49. 1570.71. 1724.51 1694.85. 2061.73. 2641.85. 2854.22. 2970.26. 3063.74. 0.00. 0.05. 0.10. Absorbance Units 0.20 0.15. 0.25. 0.30. 3449.55. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2010\atr\03\2010_08585_ARR-DE_atr01.0. 2010_08585_ARR-DE_atr01. ATR KRS-5. Page 1/1. 2010/03/22.

(9) 6-(Hidroximetilpiridina)-2-carboxilato de metilo (2) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(10) DEPT-RMN (CDCl3) (/ppm). Espectro de masas ESI+ +TOF MS: 1.183 to 1.266 min from Sample 2 (ARROH, MeOH + AcN (9+1)) of 2013_37687_ARROH_esitof_pos_01.wiff a=3.60086641316587150e-004, t0=-1.67973856138779210e+001 (Turbo Spray). Max. 4918.3 counts.. 190.05. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 168.07. 45% 40% 35% 30% 25% 20% 15% 108.04 10%. 303.09. 5% 122.06 0% 100. 120. 150.05 193.12 140. 160. 180. 206.02. 242.10 264.08. 200. 240. 220. 260. 325.08 280. 300. 320. 361.15 340 360 m/z, Da. 377.13 380 400. 420. 440. 460. 480. 500. 520. 540. 568.21 560 580. 600.

(11) 0.1. 0.2. 0.3. 0.4. Absorbance Units. 0.5. 0.6. 4000 3500. I:\ftir\ftir2013\atr\11\2013_37687_ARROH_atr01.0. 3000. 2013_37687_ARROH_atr01. 2500. ATR. 2000 1500 1000. Wavenumber cm-1 500. 2013/11/28. 353.93 313.75. 420.32. 509.18. 1215.75 1195.95 1162.38 1146.27 1093.08 1071.75 1000.60 983.15 871.52 824.96 791.45 759.40 711.35 671.49 601.78. 1291.64. 1468.74 1447.73 1435.35. 1591.58. 1740.39. 1982.50. 2955.87 2909.39. 3276.52. Espectro IR.

(12) 6-(Clorometilpiridina)-2-carboxilato de metilo (3) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).


(14) HSQC-RMN (CDCl3) (ppm). HMBC-RMN (CDCl3) (/ppm).

(15) Espectro de masas ESI+ +TOF MS: 2.736 to 3.070 min from Sample 2 (ARR4a en DCM/MeOH/ACN) of 2010_11455_ARR4a_esitof01.wiff a=3.59910337361678430e-004, t0=-1.27992566862539760e+001 (Turbo Spray). Max. 9982.9 counts.. 208.01. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 210.01. 10% 5% 0%. 126.01 120 140. 186.03 160. 180. 356.17 200. 220. 240. 260 m/z, Da. 280. 300. 320. 340. 360. 380. 400. 420. 1580.74. 1440.44 1297.98 1288.77 1261.89 1225.06 1199.62 1173.33 1152.64 1137.84 1089.21 1001.49 993.68 933.24 909.01 878.09 839.73 798.05 773.17 750.23 682.85 666.13 593.12 526.42 477.86 422.48 386.45 355.02. 1737.61 1697.76. 2020.26. 2324.09. 3066.01 3028.44 3005.45 2975.88 2953.39. 0.00. 0.05. 0.10. Absorbance Units 0.20 0.15. 0.25. 0.30. 0.35. 3460.59. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2010\atr\04\2010_11455_ARR4a_atr01.0. 2010_11455_ARR4a_atr01. ATR KRS-5. Page 1/1. 2010/04/16.

(16) Decahidro - 2a,4a,6a,8a acenaftileno (4) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm). –. tetraazaciclopenta. [fg].



(19) Espectro de masas ESI+ +TOF MS: 2.018 to 2.736 min from Sample 2 (ARR88A, MeOH/ACN/CHCl3) of 2013_03514_ARR88A_esitof01.wiff a=3.60127686632955050e-004, t0=-1.66876661615750560e+001 (Turbo Spray). Max. 4827.8 counts.. 195.16. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 196.16 217.14 110. 120. 130. 140. 150. 160. 170. 180. 190. 200. 210 m/z, Da. 220. 230. 240. 250. 260. 270. 280. 290. 300. 310. 1478.62 1463.86 1446.61 1390.10 1372.23 1346.05 1317.77 1270.56 1241.96 1216.40 1179.43 1107.69 1088.06 1060.96 1011.86 979.80 960.97 930.50 881.06 841.75 783.04 728.52 696.17 632.46 519.68 429.13. 1651.56. 2935.86 2888.13 2848.37 2792.18. 0.4 0.3 0.2 0.1 0.0. Absorbance Units. 0.5. 0.6. 3370.78. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\04\2013_09793_ARR88C_atr_01.0. 2013_09793_ARR88C_atr_01. ATR KRS-5. 2013/04/02.

(20) 2a,6a-Dibromuro de 2a,6a – dimetildodecahidro 2a,4a,6a,8a - tetraazaciclopenta [fg] acenaftileno (5) 1H-RMN. 13C-RMN. (D2O, 300 MHz) (/ppm). (D2O, 75,5 MHz) (/ppm). -.

(21) 13C-RMN. (J-MODE) (D2O) (/ppm). Espectro de masas ESI+ +TOF MS: 2.998 to 3.065 min from Sample 2 (ARRcyclenGlyBn2, MeOH) of 2014_00067_ARRcyclenGlyBn2_esitof_pos_01.wiff a=3.60095394745379940e-004, t0=-1.67449953837212640e+001 (Turbo Spray). Max. 3854.6 counts.. 285.21. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 407.28. 20% 15% 10% 5% 0% 100. 193.14 111.09 150. 200. 228.15 250. 317.23 300. 375.25 350. 400. 455.18489.25 450. 500. 550 m/z, Da. 600. 650. 700. 750. 800. 850. 900. 950. 1000.

(22) 0.00. 0.05. 0.10. 0.15. 0.20. 0.25. ATR Units. 0.30. 0.35. 0.40. 4000 3500 3000. I:\FTIR\ftir2014\atr\01\2014_00067_ARRcyclenGlyBn2_atr_01.0. 2500. 2014_00067_ARRcyclenGlyBn2_atr_01. 2000. ATR KRS-5. 1500 1000. 497.26 464.88. 1498.25 1482.89 1455.31 1435.87 1404.74 1365.99 1336.84 1287.83 1235.85 1196.93 1155.79 1101.25 1042.64 942.79 927.68 888.82 830.09 762.97 705.26 647.15. 1583.74. 2080.63. 2244.74. 2852.03. 3057.11 3006.67 2956.72. 3405.84. 3850.49. Espectro IR. Wavenumber cm-1 500. 2014/01/02.

(23) 1, 7 – Dibencil – 1, 4, 7, 10 - tetraazaciclododecano – transciclén dibencilo – (6) 1H-RMN. 13C-RMN. (CDCl3, 300 MHz) (/ppm). (CDCl3, 75,5 MHz) (/ppm).

(24) Espectro de masas ESI+ +TOF MS: 0.850 to 1.000 min from Sample 3 (Agimix) of 2014_00244_ARRcyclenBn2_esitof_pos_01.wiff a=3.60100516873410850e-004, t0=-1.64388041363187690e+001 (Turbo Spray). Max. 5635.8 counts.. 353.27. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 112.10 177.14 0% 100 150. 203.16. 263.22. 200. 250. 310.22 381.26 300 350. 411.28 400. 475.20 450. 500. 505.17 550 m/z, Da. 600. 650. 700. 750. 781.55 800. 850. 900. 950. 1000. 1492.71 1461.26 1445.67 1377.46 1354.11 1341.26 1294.56 1261.03 1202.75 1164.54 1116.05 1094.75 1063.30 1046.65 1027.92 993.70 970.73 926.83 894.82 824.94 787.40 754.42 724.22 695.55 594.63 470.90. 1644.46. 2797.82. 2933.90 2876.98. 3082.73 3060.21 3024.12. 0.5 0.4 0.3 0.2 0.1. ATR Units. 0.6. 0.7. 0.8. 3304.21. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\FTIR\ftir2014\atr\01\2014_00244_ARRCyclenBn2_atr_01.0. 2014_00244_ARRCyclenBn2_atr_01. ATR KRS-5. 2014/01/13.

(25) Diacetato de di – tert- butil 2, 2´ - (4, 10 – dibencil - 1, 4, 7, 10 – tetraazaciclododecano – 1, 7 – diil) (7) 1H-RMN. 13C-RMN. (CDCl3, 300 MHz) (/ppm). (J-MODE) (CDCl3) (/ppm).

(26) Espectro de masas ESI+ +TOF MS: 2.215 to 2.315 min from Sample 2 (ARRM3_prec, AcN) of 2014_01367_ARRM3_prec_esitof_pos_01.wiff a=3.60101539350309570e-004, t0=-1.65361509932956030e+001 (Turbo Spray). Max. 1996.9 counts.. 581.41. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 469.28. 25% 20%. 379.24. 15% 10%. 525.34 235.15. 5% 145.10171.12 246.15 263.18 291.21 150 200 250 300. 0% 100. 603.39 350. 400. 450 m/z, Da. 500. 550. 600. 650. 700. 750. 800. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\FTIR\ftir2014\atr\03\2014_06673_ARRM3_atr_01.0. 2014_06673_ARRM3_atr_01. ATR KRS-5. 2014/03/14. 322.60. 470.48. 1495.84 1451.68 1415.70 1390.07 1368.77 1347.08 1292.66 1248.87 1216.66 1154.24 1099.00 1063.12 1046.00 1032.67 1005.31 984.37 967.11 909.26 850.85 792.92 738.96 697.51 563.48. 1731.16. 2051.54. 2164.42. 2970.57 2925.67 2905.01 2837.03 2796.98. 3707.63. 0.15 0.10 0.05 0.00. ATR Units. 0.20. 0.25. 3861.24 3850.19 3834.30. Espectro IR.

(27) Diacetato de di – tert- butil 2, 2´ - (1, 4, 7, 10 – tetraazaciclododecano – 1, 7 – diil) (8) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(28) Espectro de masas ESI+ +TOF MS: 1.701 to 2.268 min from Sample 2 (ARRtransDO2AtBu, MeOH/ACN/CHCl3) of 2012_23483_ARRtransDO2AtBu_esitof01.wiff a=3.60115805777027450e-004, t0=-1.73972930344693490e+001 R; (Turbo Spray). Max. 4541.4 counts.. 401.31. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 345.25. 25% 20% 289.19 15% 10% 5% 0% 100. 120. 140. 160. 180. 200. 220. 240. 260. 280. 300. 320 340 m/z, Da. 360. 380. 403.32 400 420. 440. 460. 480. 500. 520. 540. 1731.83 1473.90 1444.06 1418.29 1390.75 1366.57 1306.27 1293.20 1257.50 1210.59 1143.52 1119.29 1104.65 1067.75 1041.38 1002.96 974.37 927.67 912.51 898.58 887.84 855.61 823.65 792.30 762.37 743.69 717.45 610.61 584.57 544.77 488.70 461.73 420.40 391.58 326.08. 2051.02. 2977.79 2930.67 2873.43 2814.62. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 3281.53. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2012\atr\09\2012_23483_ARRtransDO2AtBu_atr01.0. 2012_23483_ARRtransDO2AtBu_atr01. Page 1/1. ATR KRS-5. 2012/09/04.

(29) Diacetato de di – tert- butil 2, 2´ - (4 – metil - 1, 4, 7, 10 – tetraazaciclododecano – 1, 7 – diil) (9) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(32) Espectro de masas ESI+ +TOF MS: 1.284 to 1.918 min from Sample 2 (ARR86AMPLCA, MeOH/ACN/CHCl3) of 2012_30424_ARR86AMPLCA_esitof01.wiff a=3.60113149897449180e-004, t0=-1.67157584431136780e+001 (Turbo Spray). Max. 3480.3 counts.. 415.33. 100% 95% 90% 303.20. 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 359.27. 20% 15% 10% 5% 0% 100. 135.05 120. 140. 160. 180. 200. 220. 240. 260. 280. 300. 320 340 m/z, Da. 360. 380. 400. 420. 440. 460. 480. 500. 520. 540. 1715.30 1530.75 1457.47 1445.63 1421.80 1396.14 1369.68 1330.50 1293.78 1274.35 1255.66 1221.49 1160.46 1146.72 1111.89 1095.43 1078.17 1049.99 1024.65 988.91 956.54 939.02 919.63 899.29 848.42 809.93 787.13 743.58 648.21 584.76 548.01 535.63 434.16 396.37 363.19 324.42. 2050.11. 1981.08. 2325.00. 0.15 0.10 0.05. Absorbance Units. 0.20. 0.25. 0.30. 2945.40. 2874.84 2811.41. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2012\atr\11\2012_30424_ARR86A-MPLCA_atr_01.0. 2012_30424_ARR86A-MPLCA_atr_01. Page 1/1. ATR KRS-5. 2012/11/21.

(33) Diacetato de di – tert- butil 2, 2´ - (4 – ((6 – (metoxicarbonil)piridin – 2 il) – 10 – metil - 1, 4, 7, 10 – tetraazaciclododecano – 1, 7 – diil) (10) 1H-RMN. 13C-RMN. (CDCl3, 300 MHz) (/ppm). (CDCl3, 75,5 MHz) (/ppm).

(34) Espectro de masas ESI+ +TOF MS: 1.350 to 1.851 min from Sample 2 (ARR101A, MeOH/CHCl3) of 2013_02588_ARR101A_esitof01.wiff a=3.60125800879986610e-004, t0=-1.69223139975846340e+001 (Turbo Spray). Max. 3195.1 counts.. 564.37. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 150. 200. 250. 300. 350. 400. 452.26 450. 508.32 500 m/z, Da. 586.36 602.33 550. 600. 737.37 650. 700. 750. 800. 850. 900. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\02\2013_02587_ARR101A_atr_01.0. 2013_02587_ARR101A_atr_01. ATR KRS-5. 2013/02/01. 327.13. 677.82 659.44 633.72 577.22. 847.96 800.88 747.36. 1035.96 1011.78 976.37. 1221.22. 1152.08 1107.86. 1454.30 1392.04 1367.21 1306.20. 1726.47. 1589.66. 2816.53. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 2977.65 2929.12. Espectro IR.

(35) Ácido 2, 2´ - (4 – ((6 –carboxipiridin – 2 il)metil) – 10 – metil - 1, 4, 7, 10 – tetraazaciclododecano – 1, 7 – diil) diacético (1,7–H3Medo2apa·7HCl·3H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 0,8) (/ppm). (D2O, 125,8 MHz, pD = 0,8) (/ppm).

(36) DEPT-RMN (D2O, pD = 0,8) (/ppm). COSY-RMN (D2O, pD = 0,8) (/ppm).

(37) HSQC-RMN (D2O, pD = 0,8) (/ppm). HMBC-RMN (D2O, pD = 0,8) (/ppm).

(38) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 7,1) (/ppm). (D2O, 125,8 MHz, pD = 7,1) (/ppm).



(41) Espectro de masas ESI+ +TOF MS: 1.050 to 1.718 min from Sample 2 (ARR108, MeOH) of 2013_01904_ARR108_esitof01.wiff a=3.60114217271908610e-004, t0=-1.70471340476654060e+001 R; (Turbo Spray). Max. 1136.9 counts.. 438.23. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0%. 492.15. 219.62 150. 200. 250. 300. 350. 400 m/z, Da. 450. 500. 550. 600. 650. 700. 1738.00 1618.44 1522.61 1460.94 1411.61 1390.92 1335.34 1291.13 1269.21 1215.43 1169.72 1123.08 1079.27 1045.95 1032.64 1016.23 984.92 954.22 938.67 916.57 901.19 865.58 843.11 760.05 744.50 715.14 653.76 624.17 605.25 540.67 516.56 484.67 449.01 430.59 406.16 348.27 340.65. 1981.81. 2051.20. 2593.19. 2685.00. 2841.00. 3357.04. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 3813.37. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\04\2013_13198_ARR108A_atr_01.0. 2013_13198_ARR108A_atr_01. ATR KRS-5. 2013/04/25.

(42) Ácido 2, 2´ - (4 – ((6 –carboxipiridin – 2 il)metil) – 10 – metil - 1, 4, 7, 10 – tetraazaciclododecano – 1, 7 – diil) diacético (1,7–H3Medo2apa·8TFA·H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 1,2) (/ppm). (D2O, 125,8 MHz, pD = 1,2) (/ppm).



(45) +TOF MS: 1.050 to 1.718 min from +TOF MS:21.050 to 1.718 minoffrom Sample Sample 2 (ARR108, MeOH) of 2013_01904_ARR108_esitof01.wiff (ARR108, MeOH) 2013_01904_ARR108_esitof01.wiff +TOF MS: 1.050 to 1.718 min from Sample 2 (ARR108, MeOH) of 2013_01904_ARR108_esitof01.wiff a=3.60114217271908610e-004, a=3.60114217271908610e-004,R; t0=-1.70471340476654060e+001 t0=-1.70471340476654060e+001 R; (Turbo Spray) (Turbo Spray) a=3.60114217271908610e-004, t0=-1.70471340476654060e+001 R; (Turbo Spray) 438.23 100% 100% 438.23 100% 95% 95% 95% 90% 90% 90% 85% 85% 85% 80% 80% 80% 75% 75% 75% 70% 70% 70% 65% 65% 65% 60% 60% 60% 55% 55% 55% 50% 50% 50% 45% 45%. 45%. 40%. 40%. 35%. 35%. 30%. 30%. 25%. 25%. 20%. 20%. 15%. 15%. 10%. 10%. 10%. 5%. 5%. 5%. 0% 219.62. 40% 35% 30% 25% 20% 15%. 0%. 150. Max. 1136.9 counts.. 438.23. 200. 219.62 0% 200. 150. 250. 300. 492.15. 219.62 150 250. 350. 200 300. 400 m/z, Da. 250 492.15 400 300 350 m/z, Da 450 500. 450350. 550. 492.15. 500400 550450 m/z, Da 600 650. 600500. 700. 1738.00 1618.44 1522.61 1460.94 1411.61 1390.92 1335.34 1291.13 1269.21 1215.43 1169.72 1123.08 1079.27 1045.95 1032.64 1016.23 984.92 954.22 938.67 916.57 901.19 865.58 843.11 760.05 744.50 715.14 653.76 624.17 605.25 540.67 516.56 484.67 449.01 430.59 406.16 348.27 340.65. 1981.81. 2051.20. 2593.19. 2685.00. 2841.00. 3357.04. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 3813.37. Espectro IR. 4000. Max. 11. Max. 1136.9 counts.. R e l. I n t . ( % ). R e l. I n t . ( % ). R e l. I n t . ( % ). Espectro de masas ESI+. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\04\2013_13198_ARR108A_atr_01.0. 2013_13198_ARR108A_atr_01. ATR KRS-5. 2013/04/25. 650 550. 700 600. 650.

(46) 2a - Yoduro de 2a - metildodecahidro – 1H - 2a,4a,6a,8a – tetraazaciclopenta[fg]acenaftileno - yoduro de 1 - metil ciclén glioxal – (11) 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(47) DEPT-RMN (D2O) (/ppm). COSY-RMN (D2O) (/ppm).

(48) HSQC-RMN (D2O) (/ppm). HMBC-RMN (D2O) (/ppm).

(49) 0.05. 0.10. 0.15. 0.20. 0.25. Absorbance Units. 0.30. 0.35. 4000 120 140 160 180. 3500. I:\ftir\ftir2013\atr\04\2013_12586_ARR134_atr_01.0. 200 220. 3000 240 260. 2352.04 2325.02 2164.77 2114.10 2051.92 1982.10 1714.10 1670.20 1556.26 1538.04 1486.14 1465.39 1450.70 1415.63 1405.52 1376.00 1342.27 1327.12 1317.48 1296.29 1264.19 1220.05 1200.38 1177.74 1151.46 1137.50 1119.20 1087.62 1045.99 1016.13 988.57 944.47 915.88 905.82 851.33 815.59 784.66 767.07 755.93 725.46 699.20 620.48 579.68 522.77 493.45 451.19 418.11 395.58 368.95 359.41 348.56 318.48. R e l. I n t . ( % ). 100%. 3012.89 2999.88 2941.88 2905.38 2848.74 2816.95. 0% 100. 3193.59. 3898.46 3861.74 3850.32 3834.91 3813.67 3742.19 3731.42 3708.32 3686.45 3667.48 3645.98 3626.08 3509.58 3343.81. Espectro de masas ESI+ +TOF MS: 2.587 to 2.787 min from Sample 5 (arr134) of 2013_12586_arr134_esitof_pos_01.wiff a=3.60120643663495190e-004, t0=-1.64473616018101690e+001 (Turbo Spray). 280. 2013_12586_ARR134_atr_01. 300 320 340. 2500. ATR KRS-5. Max. 2505.1 counts.. 209.17. 95%. 90%. 85%. 80%. 75%. 70%. 65%. 60%. 55%. 50%. 45%. 40%. 35%. 30%. 25%. 20%. 15%. 10%. 5%. 360 380 m/z, Da. 2000 400 420 440 460. 1500 480 500 520. 1000. 540 560 580 600. Espectro IR. Wavenumber cm-1. 500. 2013/04/19.

(50) 1 – Metil – 1,4,7,10 – tetraazaciclododecano (12) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(53) Espectro de masas ESI+ +TOF MS: 1.732 to 1.882 min from Sample 3 (ARR136) of 2013_16080_ARR136_esitof_pos_01.wiff a=3.60136869953353060e-004, t0=-1.62253882381463900e+001 (Turbo Spray). Max. 1483.3 counts.. 187.19. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 120. 140. 160. 180. 200. 220. 240. 260 m/z, Da. 280. 300. 320. 340. 360. 380. 400. 1981.73. 1481.40 1457.94 1442.83 1352.33 1341.22 1309.43 1287.19 1271.01 1254.07 1244.18 1219.07 1188.68 1165.54 1151.67 1128.83 1107.60 1082.64 1062.71 1041.12 1029.28 1012.26 975.00 943.15 920.97 905.36 886.59 861.46 829.35 794.62 781.50 742.81 590.30 562.19 537.61 498.73 449.80 408.63 356.81 333.05. 2324.62. 2701.23. 2973.67 2929.65 2886.98 2829.40 2786.57. 0.5 0.4 0.3 0.2 0.1 0.0. Absorbance Units. 0.6. 0.7. 3302.01 3270.13. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\05\2013_15348_ARR136_atr01.0. 2013_15348_ARR136_atr01. ATR KRS-5. 2013/05/10.

(54) Metil 6 - ((4 – metil - 1,4,7,10 – tetraazaciclododecan – 1 il)metil)picolinato (13) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(57) Espectro de masas ESI+ +TOF MS: 1.235 to 1.319 min from Sample 2 (ARRM7B, MeOH) of 2014_07371_ARRM7B_esitof_pos_01.wiff a=3.60048738199850230e-004, t0=-1.49807397746590160e+001 R; (Turbo Spray). Max. 2516.5 counts.. 336.25. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 348.24. 5% 110.05168.62 0% 100 150 200. 250.16 250. 360.18 380.27 300. 350. 400. 634.36 450. 500. 550 600 m/z, Da. 650. 700. 750. 800. 850. 900. 950. 1000. 760.92. 1227.53 1193.75 1136.60. 1454.94. 1315.44. 1587.71. 1722.09. 2801.57. 2949.38. 0.06 0.04 0.02 0.00. ATR Units. 0.08. 0.10. 0.12. 3426.69. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\FTIR\ftir2014\atr\03\2014_07371_ARRM7B_atr_01.0. 2014_07371_ARRM7B_atr_01. ATR KRS-5. 2014/03/25.

(58) Diacetato de di-tert-butil 2,2' - (7 - ((6 (metoxicarbonil)piridin – 2 - il)metil)-10-metil - 1,4,7,10 – tetraazaciclododecano - 1,4 - diil) (14) 1H-RMN. 13C-RMN. (CDCl3, 300 MHz) (/ppm). (CDCl3, 75,5 MHz) (/ppm).

(59) Espectro de masas ESI+ +TOF MS: 1.402 to 1.502 min from Sample 2 (ARRM8, MeOH) of 2014_07373_ARRM8_esitof_pos_01.wiff a=3.60049778716180710e-004, t0=-1.56872175888596210e+001 R; (Turbo Spray). Max. 3935.4 counts.. 564.37. 100% 95% 90%. 586.35. 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15%. 529.39. 10% 5% 0% 100. 450.31 508.33 551.39. 394.26 415.34 150. 200. 250. 300. 350. 400. 450. 500. 550 600 m/z, Da. 650. 700. 750. 800. 850. 900. 950. 1000. 326.63. 644.18. 849.60. 758.93 727.03. 992.01. 911.49. 1392.03 1366.96 1292.90 1254.48 1220.32 1149.51. 1589.46. 1455.15. 1724.46. 2229.49. 2800.42. 0.25 0.20 0.15 0.10 0.05 0.00. ATR Units. 0.30. 0.35. 0.40. 2976.30 2933.49. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\FTIR\ftir2014\atr\03\2014_07373_ARRM8_atr_01.0. 2014_07373_ARRM8_atr_01. ATR KRS-5. 2014/03/26.

(60) Ácido 2, 2´ - (7 – ((6 –carboxipiridin – 2 il)metil) – 10 – metil - 1, 4, 7, 10 – tetraazaciclododecano – 1, 4 – diil) diacético (1,4–H3Medo2apa·5HCl·2H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD ~ 7) (/ppm). (D2O, 125,8 MHz, pD ~ 7) (/ppm).

(61) DEPT-RMN (D2O, pD ~ 7) (/ppm). COSY-RMN (D2O, pD ~ 7) (/ppm).

(62) HSQC-RMN (D2O, pD ~ 7) (/ppm). HMBC-RMN (D2O, pD ~ 7) (/ppm).

(63) Espectro de masas ESI+ +TOF MS: 2.399 to 2.615 min from Sample 2 (ARR148C2, AcN) of 2014_03905_ARR148C2_esitof_pos_01.wiff a=3.60101590005543920e-004, t0=-1.62802410298959930e+001 R; (Turbo Spray). Max. 1373.9 counts.. 438.24. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 380.23. 40% 35% 30% 25% 20% 15% 10%. 460.21. 5% 0% 100. 131.58 150. 322.22 336.24394.24 236.14 280.13 200 250 300 350 400. 179.08. 424.22482.19515.26 450. 500. 550 m/z, Da. 600. 650. 700. 750. 800. 875.45 850 900. 950. 1000. 659.59. 762.96. 1082.81. 1180.55. 1384.78. 1462.13. 1593.22. 1714.32. 2051.26. 2849.01. 3369.97. 0.20 0.15 0.10 0.05. ATR Units. 0.25. 0.30. 0.35. 3698.49. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2014\atr\03\2014_07367_ARRM8H_atr_01.0. 2014_07367_ARRM8H_atr_01. ATR KRS-5. 2014/03/25.

(64) Di – tert - butil 1,4,7,10 – tetraazaciclododecano - 1,7 dicarboxilato (15) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(67) Espectro de masas ESI+ +TOF MS: 1.167 to 1.567 min from Sample 2 (ARR91, MeOH/ACN/CH2Cl2) of 2012_31870_ARR91_esitof01.wiff a=3.60109419380827220e-004, t0=-1.66271771196770710e+001 (Turbo Spray). Max. 897.0 counts.. 373.28. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 385.28 0% 100. 150. 200. 250. 300. 350. 781.54. 400. 450. 500 550 m/z, Da. 600. 650. 700. 750. 800. 845.62 850. 900. 1461.67 1405.58 1365.04 1323.98 1274.20 1248.08 1214.12 1159.07 1118.84 1084.31 1065.46 1028.19 1012.02 979.02 962.09 942.53 906.62 857.35 775.12 758.60 731.76 700.36 625.33 554.34 499.43 460.90 402.09 336.07. 1685.85. 2973.77 2932.43. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 3419.54. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2012\atr\12\2012_31870_ARR91_atr_01.0. 2012_31870_ARR91_atr_01. ATR KRS-5. 2012/12/11.

(68) Di – tert - butil 4,10-bis ((6-(metoxicarbonil)piridina – 2 il)metil) - 1,4,7,10-tetraazaciclododecano - 1,7 dicarboxilato (16) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm) (328,5 K), sonda bbi.

(69) 13C-RMN. (CDCl3, 125,8 MHz) (/ppm). Espectro de masas ESI+ +TOF MS: 0.599 to 1.484 min from Sample 2 (ARR42 en MeOH / DCM / CH3CN) of 2011_10649_ARR42_esitof01.wiff a=3.59923594884105680e-004, t0=-1.34576531820864510e+001 (Turbo Spray). Max. 2576.4 counts.. 671.37. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0%. 150. 200. 250. 300. 350. 400. 450. 500. 550 m/z, Da. 600. 650. 700. 750. 800. 850. 900. 950. 1000.

(70) 0.0. 0.1. 0.2. 0.3. Absorbance Units. 0.4. 0.5. 4000 3500. I:\ftir\ftir2011\atr\03\2011_10649_ARR42_atr01.0. 3000. 2011_10649_ARR42_atr01. 2500 2000. ATR KRS-5. Page 1/1. 1477.56 1453.72 1409.45 1389.38 1364.31 1315.47 1271.92 1247.07 1148.74 1136.88 1046.06 994.09 977.50 960.73 915.83 890.50 858.09 835.96 799.94 754.60 678.11 634.15 555.60 515.75 461.34 422.29 404.38 364.83. 1588.77. 1742.66 1722.99 1681.87. 2361.39. 2809.23. 2973.69. 3602.73. Espectro IR. Wavenumber cm-1 1500 1000 500. 2011/03/31.

(71) Ácido 6,6´ - ((1,4,7,10 – tetraazaciclododecano - 1,7 - diil) bis -(metilen))dipicolínico (H2dodpa·5HCl·4H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 0,7) (/ppm). (D2O, 125,8 MHz, pD = 0,7) (/ppm).


(73) HSQC-RMN (D2O, pD = 0,7) (ppm). HMBC-RMN (D2O, pD = 0,7) (/ppm).




(77) Espectro de masas ESI+ +TOF MS: 1.234 to 2.152 min from Sample 2 (ARR6b en MeOH / DCM / CH3CN) of 2010_17588_ARR6b_esitof01.wiff a=3.59913621835560810e-004, t0=-1.26102543070667340e+001 (Turbo Spray). Max. 3206.0 counts.. 443.25. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50%. 222.13. 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 199.12 213.12 133.08. 191.60 204.12. 150. 200. 399.26. 308.21 250. 300. 350. 400 m/z, Da. 450. 500. 550. 600. 650. 700. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 477.13. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\11\2013_35837_ARR112_atr01.0. 2013_35837_ARR112_atr01. ATR KRS-5. 2013/11/11. 374.92 321.40. 761.88. 993.38. 1085.65. 1282.85 1228.52 1171.32. 1439.58 1396.81. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 0.5. 1632.64. 3356.79. Espectro IR.

(78) Ácido 6,6´ - ((1,4,7,10 – tetraazaciclododecano - 1,7 - diil) bis -(metilen))dipicolínico (H2dodpa·5TFA) 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(79) Espectro de masas ESI+ +TOF MS: 1.234 to 2.152 min from Sample 2 (ARR6b en MeOH / DCM / CH3CN) of 2010_17588_ARR6b_esitof01.wiff a=3.59913621835560810e-004, t0=-1.26102543070667340e+001 (Turbo Spray). Max. 3206.0 counts.. 443.25. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50%. 222.13. 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 199.12 213.12 133.08. 191.60 204.12. 150. 200. 399.26. 308.21 250. 300. 350. 400 m/z, Da. 450. 500. 550. 600. 650. 700. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 477.13. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\11\2013_35837_ARR112_atr01.0. 2013_35837_ARR112_atr01. ATR KRS-5. 2013/11/11. 374.92 321.40. 761.88. 993.38. 1085.65. 1282.85 1228.52 1171.32. 1439.58 1396.81. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 0.5. 1632.64. 3356.79. Espectro IR.

(80) 2a,6a - Diyoduro de 2a,6a – dimetildodecahidro 2a,4a,6a,8a – tetraazaciclopenta [fg] acenaftileno (17) 1H-RMN. 13C-RMN. (D2O, 300 MHz) (/ppm). (D2O, 75,5 MHz) (/ppm).

(81) Espectro de masas ESI+ +TOF MS: 1.717 to 2.418 min from Sample 2 (CPI01, DCM/MeOH/ACN) of 2010_39557_CPI01_esitof02.wiff a=3.59923788157551220e-004, t0=-1.34880807738807120e+001 (Turbo Spray) 100%. Max. 5668.5 counts.. 112.10. 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60%. 351.10. 55% 50% 45% 40% 209.18. 35% 30% 25% 20% 111.09. 337.19. 15% 10% 5% 0% 100. 154.13. 150. 354.27. 251.18 200. 674.98. 277.24 291.26. 223.19. 132.90. 250. 300. 381.30. 350. 443.33. 400. 683.55 711.58. 456.40. 450 m/z, Da. 500. 550. 600. 650. 700. 750. 800. 1693.77 1462.07 1449.16 1413.71 1393.69 1362.59 1334.91 1312.53 1290.26 1228.81 1200.06 1177.70 1142.93 1099.71 1078.84 1036.85 1017.92 1008.68 977.59 934.61 926.09 903.44 849.20 769.83 664.95 628.31 585.97 567.43 516.66 489.50 459.34 442.30 421.35 391.03 360.37 321.16. 1981.33. 2051.28. 2324.30. 2848.05. 2999.20 2987.72 2952.97. 3667.33 3645.58. 3742.19. 0.15 0.10 0.05 0.00. Absorbance Units. 0.20. 0.25. 3861.50 3850.47. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2010\atr\12\2010_39557_CPI-01_atr01.0. 20101230_CPI-01_atr01. ATR KRS-5. Page 1/1. 2010/12/30.

(82) 1,7-Dimetil-1,4,7,10-tetraazaciclododecano (18) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(83) Espectro de masas ESI+ +TOF MS: 1.484 to 2.001 min from Sample 2 (ARR103, MeOH/ACN/CHCl3) of 2012_31291_ARR103_esitof01.wiff a=3.60115033090907390e-004, t0=-1.65699807431133620e+001 (Turbo Spray). Max. 785.7 counts.. 201.21. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 202.21 213.21 110. 120. 130. 140. 150. 160. 170. 180. 190. 200. 210 220 m/z, Da. 230. 240. 250. 260. 270. 280. 290. 300. 310. 320. 443.41 391.21 354.51 331.21. 1354.25 1341.72 1289.83 1236.89 1207.79 1187.45 1161.48 1117.27 1088.41 1055.48 1035.82 989.92 959.44 936.05 904.34 806.50 787.03 737.31 590.68 533.66. 1458.67. 1666.69. 2882.62 2835.82 2794.45. 2946.88. 0.20 0.15 0.10 0.05 0.00. Absorbance Units. 0.25. 0.30. 0.35. 3287.25. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2012\atr\11\2012_31291_ARR103_atr01.0. 2012_31291_ARR103_atr01. ATR KRS-5. Page 1/1. 2012/11/29.

(84) Dimetil 6,6´ - ((4,10 – dimetil - 1,4,7,10 – tetraazaciclododecano - 1,7 - diil)bis(metilen))dipicolinato (19) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(85) DEPT-RMN (CDCl3) (/ppm). HSQC-RMN (CDCl3) (/ppm).

(86) +TOF MS: 0.533 to 0.983 min from Sample 2 (CPI17, MeOH/DCM/ACN) of 2010_39565_CPI17_esitof01.wiff a=3.59923788157551220e-004, t0=-1.34880807738807120e+001 (Turbo Spray). Max. 540.3 counts.. 499.31. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45%. 521.29. 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 513.32 200. 300. 400. 500. 600. 700. 800. 900. 1000 1100 m/z, Da. 1200. 1300. 1400. 1500. 1600. 1700. 1800. 1900. 2000. 1716.27 1588.76 1456.83 1439.26 1428.91 1359.77 1309.84 1293.59 1258.77 1244.61 1229.08 1191.60 1158.93 1139.59 1085.97 1068.17 1058.54 1038.93 1008.96 991.61 972.54 927.24 887.03 830.30 806.11 796.02 760.97 715.85 681.31 624.39 570.17 559.38 520.20 454.82 429.00 396.00 360.47 343.10. 2809.89. 2967.77 2946.77 2895.92. 3053.99. 0.05. 0.10. 0.15. 0.20. 0.25. 0.30. 0.35. 0.40. 3410.80. Espectro IR. 0.00. Absorbance Units. Espectro de masas ESI+. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2010\atr\12\2010_39565_CPI-17_atr01.0. 2010_59565_CPI-17_atr01. ATR KRS-5. Page 1/1. 2010/12/30.

(87) Ácido dimetil 6,6´ - ((4,10 – dimetil - 1,4,7,10 – tetraazaciclododecano - 1,7 - diil)bis(metilen))dipicolínico (H2Me2DODPA·7HCl·H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 0,8) (/ppm). (D2O, 125,8 MHz, pD = 0,8) (/ppm).






(93) Espectro de masas ESI+ +TOF MS: 2.552 to 3.019 min from Sample 2 (CPI09, DCM/MeOH/ACN) of 2010_39560_CPI09_esitof01.wiff a=3.59923788157551220e-004, t0=-1.34880807738807120e+001 (Turbo Spray). Max. 4877.7 counts.. 236.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35%. 533.18. 30% 25% 471.27. 20% 15% 10%. 509.22. 179.08. 5% 0% 100. 131.58. 160.11 150. 220.62 227.14 267.10 200. 250. 300. 350 m/z, Da. 537.18. 525.19. 398.16. 326.24. 400. 450. 500. 550. 600. 525.85 420.81 356.59 343.11 317.50 307.93. 758.80 713.09 653.58 625.27. 889.81 835.61. 1007.66 952.49. 1139.38 1080.10. 1523.67. 1455.58 1403.87 1346.78 1320.32 1260.88 1210.45. 1730.25. 1615.10. 1981.21. 2164.89. 2051.43. 2657.57. 2965.65. 3359.30. 3731.75 3686.54 3667.39 3646.15. 0.10 0.05 0.00. Absorbance Units. 0.15. 0.20. 3850.65. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2011\atr\04\2011_13479_ARR47_atr01.0. 2011_13479_ARR47_atr01. ATR KRS-5. Page 1/1. 2011/04/18.

(94) Ácido dimetil 6,6´ - ((4,10 – dimetil - 1,4,7,10 – tetraazaciclododecano - 1,7 - diil)bis(metilen))dipicolínico (H2Me2DODPA·11TFA) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 0,8) (/ppm). (D2O, 125,8 MHz, pD = 0,8) (/ppm).

(95) Espectro de masas ESI+ +TOF MS: 2.552 to 3.019 min from Sample 2 (CPI09, DCM/MeOH/ACN) of 2010_39560_CPI09_esitof01.wiff a=3.59923788157551220e-004, t0=-1.34880807738807120e+001 (Turbo Spray). Max. 4877.7 counts.. 236.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35%. 533.18. 30% 25% 471.27. 20% 15% 10%. 509.22. 179.08. 5% 0% 100. 131.58. 160.11 150. 220.62 227.14 267.10 200. 250. 300. 350 m/z, Da. 537.18. 525.19. 398.16. 326.24. 400. 450. 500. 550. 600. 525.85 420.81 356.59 343.11 317.50 307.93. 758.80 713.09 653.58 625.27. 889.81 835.61. 1007.66 952.49. 1139.38 1080.10. 1523.67. 1455.58 1403.87 1346.78 1320.32 1260.88 1210.45. 1730.25. 1615.10. 1981.21. 2164.89. 2051.43. 2657.57. 2965.65. 3359.30. 3731.75 3686.54 3667.39 3646.15. 0.10 0.05 0.00. Absorbance Units. 0.15. 0.20. 3850.65. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2011\atr\04\2011_13479_ARR47_atr01.0. 2011_13479_ARR47_atr01. ATR KRS-5. Page 1/1. 2011/04/18.

(96) 1,4,8,11-tetraazatriciclo[9.3.1.14,8]hexadecano (20) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(97) Espectro de masas ESI+ +TOF MS: 1.982 to 2.098 min from Sample 2 (MARR1, MeOH) of 2013_38989_MARR1_esitof_pos_01.wiff a=3.60090992470250920e-004, t0=-1.66933960024958560e+001 (Turbo Spray). Max. 4250.8 counts.. 225.21. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 111.09125.11 0% 100 120 140. 160. 180. 196.17 200. 227.21 220. 240. 260. 280. 301.14 300 320 m/z, Da. 340. 360. 380. 400. 420. 440. 460. 480. 500. 1472.16 1456.30 1445.57 1395.96 1377.37 1353.10 1317.14 1291.87 1262.33 1222.38 1195.19 1184.52 1131.93 1106.84 1077.91 1061.80 1031.57 1010.03 975.04 927.29 902.43 879.07 784.23 758.14 657.00 560.80 514.73 485.10 462.33 381.16. 1651.28. 2196.65. 2807.00 2769.75. 3039.07. 2958.30 2937.05 2880.57. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 0.5. 3221.47. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\12\2013_38990_MARR1_atr_01.0. 2013_38990_MARR1_atr_01. ATR KRS-5. 2013/12/11.

(98) 1,8-diyoduro de 1,8 – dimetil - 1,4,8,11 – tetraazatriciclo [9.3.1.14,8] hexadecano (21) 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(99) Espectro de masas ESI+ +TOF MS: 1.199 to 1.299 min from Sample 2 (MARR2, MeOH) of 2013_39033_MARR2_esitof_pos_01.wiff a=3.60090992470250920e-004, t0=-1.66933960024958560e+001 (Turbo Spray). Max. 2138.4 counts.. 253.24. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 381.15. 60% 55% 229.24 50% 45% 40% 35%. 239.22. 30% 25% 20% 285.27 15% 127.12 10% 5% 0% 100. 105.60. 242.24. 329.25. 367.23 509.47 537.51. 200. 300. 400. 500. 887.61 600. 700. 800 m/z, Da. 1187.57. 900. 1000. 1100. 1200. 1300. 1400. 1500. 1472.16 1456.30 1445.57 1395.96 1377.37 1353.10 1317.14 1291.87 1262.33 1222.38 1195.19 1184.52 1131.93 1106.84 1077.91 1061.80 1031.57 1010.03 975.04 927.29 902.43 879.07 784.23 758.14 657.00 560.80 514.73 485.10 462.33 381.16. 1651.28. 2196.65. 2807.00 2769.75. 2958.30 2937.05 2880.57. 3039.07. 0.3 0.2 0.1 0.0. Absorbance Units. 0.4. 0.5. 3221.47. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\12\2013_38990_MARR1_atr_01.0. 2013_38990_MARR1_atr_01. ATR KRS-5. 2013/12/11.

(100) 1,8-dimetil-1,4,8,11-tetraazaciclododecano (22) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(103) +TOF MS: 0.900 to 1.868 min from Sample 2 (ARRtranscyclamMe2, MeOH/ACN/DCM/CHCl3) of 2012_30891_ARRtranscyclamMe2_esitof0... a=3.60116663918206010e-004, t0=-1.66136168746710310e+001 (Turbo Spray). Max. 8060.9 counts.. 229.24. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 110. 120. 130. 140. 150. 160. 170. 180. 190. 200. 210. 220. 230 240 m/z, Da. 250. 260. 270. 280. 290. 300. 310. 320. 330. 340. 350. 1659.31 1463.26 1348.61 1334.64 1298.38 1265.46 1241.79 1225.01 1198.83 1183.00 1167.67 1135.31 1100.13 1085.27 1045.14 977.33 939.82 904.97 881.20 801.74 757.38 737.15 580.59 542.64 517.51 414.23 396.32 359.79 346.37 338.37 330.47 317.87. 1969.35. 2175.79. 2875.42 2834.73 2786.56. 2941.73. 3291.53. 0.05. 0.10. 0.15. 0.20. 3744.33. Espectro IR. 0.00. Absorbance Units. Espectro de masas ESI+. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2012\atr\11\2012_30891_ARRtranscyclam_Me2_atr01.0. 2012_30891_ARRtranscyclam_Me2_atr01. Page 1/1. ATR KRS-5. 2012/11/27.

(104) Dimetil 6,6' - ((4,11 – dimetil tetraazaciclotetradecano 1,8 bis(metilen))dipicolinato (23) 1H-RMN. 13C-RMN. (CDCl3, 300 MHz) (/ppm). (CDCl3, 75,5 MHz) (/ppm). 1,4,8,11 – diil).

(105) Espectro de masas ESI+ +TOF MS: 0.833 to 1.751 min from Sample 3 (CPIEA, MeOH/DCM/ACN) of 2010_39566_CPIEA_esitof01.wiff a=3.59923788157551220e-004, t0=-1.34880807738807120e+001 (Turbo Spray). Max. 4948.5 counts.. 527.33. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 541.36 150. 200. 250. 300. 350. 400. 450 m/z, Da. 500. 550. 600. 650. 700. 750. 800. 1732.60 1707.00 1614.26 1587.79 1455.09 1392.06 1369.24 1306.47 1276.79 1222.51 1171.10 1133.33 1107.09 1091.86 1075.64 1027.19 993.25 982.21 962.83 918.58 890.50 863.90 841.54 762.50 722.09 681.67 637.65 578.01 541.25 489.94 449.40 421.24 395.57 358.43 346.94 335.45 314.67. 1982.16. 2051.13. 2166.03. 2324.00. 2780.55. 2976.61 2955.34 2931.30 2849.04. 3054.94. 0.25 0.20 0.15 0.10 0.05. Absorbance Units. 0.30. 0.35. 3898.07 3850.54 3834.03 3814.11 3798.05 3742.25 3731.97 3708.15 3686.20 3667.15 3645.85 3626.13 3404.90. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\07\2013_26848_ARR162_atr_01.0. 2013_26848_ARR162_atr_01. ATR KRS-5. 2013/08/01.

(106) Ácido 6,6' - ((4,11 – dimetil tetraazaciclotetradecano - 1,8 - diil) dipicolínico (H2Me2tedpa·5HCl·3H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 0,7) (/ppm). (CDCl3, 125,8 MHz, pD = 0,7) (/ppm). 1,4,8,11 – bis(metilen)).






(112) Espectro de masas ESI+ +TOF MS: 0.583 to 1.284 min from Sample 2 (CPI12, MeOH/DCM/ACN) of 2010_39562_CPI12_esitof01.wiff a=3.59923788157551220e-004, t0=-1.34880807738807120e+001 (Turbo Spray). Max. 3340.7 counts.. 250.16. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 499.31. 30% 25% 20% 15% 10% 5% 0% 100. 193.10 138.59 149.11 150. 206.17 200. 257.17 250. 340.26 350. 300. 400 m/z, Da. 450. 500. 553.23 550. 600. 650. 700. 1750.32 1649.33 1595.92 1573.11 1478.10 1463.10 1414.06 1381.00 1340.91 1253.01 1236.02 1211.05 1187.43 1153.28 1084.34 1069.39 1033.71 1001.42 979.76 963.31 881.11 861.68 836.78 784.80 755.39 718.45 663.32 636.37 605.44 578.36 532.60 512.03 469.84 424.31 390.68 352.08 336.73. 1981.06. 2050.96. 2486.97. 2582.46. 2998.44 2939.08. 3188.95. 3353.68. 0.20 0.15 0.10 0.05 0.00. Absorbance Units. 0.25. 0.30. 0.35. 3463.47 3427.84. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2010\atr\12\2010_39562_CPI-12_atr01.0. 2010_59562_CPI-12_atr01. ATR KRS-5. Page 1/1. 2010/12/30.

(113) Decahidro - 1H,6H - 3a,5a,8a,10a - tetraazapireno – ciclam-glioxal – (24) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(114) DEPT-RMN (CDCl3, 500 MHz) (/ppm). Espectro de masas ESI+ +TOF MS: 2.570 to 3.037 min from Sample 4 (ARR72) of 2013_08209_ARR72_esitof_pos_01.wiff a=3.60138615485831270e-004, t0=-1.63724597704371000e+001 (Turbo Spray). Max. 9251.8 counts.. 223.20. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 245.18 0% 100. 120. 140. 160. 180. 200. 220. 240. 260. 280. 300 320 m/z, Da. 340. 360. 380. 400. 420. 440. 460. 480. 500.

(115) 0.0. 0.1. 0.2. 0.3. 0.4. 0.5. Absorbance Units. 0.6. 0.7. 0.8. 4000 3500. I:\ftir\ftir2013\atr\03\2013_08209_ARR72_atr_01.0. 2937.92. 3000. 2013_08209_ARR72_atr_01. 2500. ATR KRS-5. 2000 1500. 1353.97 1340.37 1297.79 1251.51 1240.81 1222.78 1144.18 1101.51 1078.70 1065.32 1035.91 993.75 961.02 942.58 906.61 857.31 825.84 796.86 781.47 725.09 639.58 593.39 524.02 480.91. 1462.66 1442.32. 2194.20. 2860.88 2813.04 2753.60. Espectro IR. Wavenumber cm-1 1000 500. 2013/03/21.

(116) 3a,8a - dibromuro de 3a,8a – dibenciltetradecahidro 3a,5a,8a,10a – tetraazapireno (25) 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(117) DEPT-RMN (CDCl3, 500 MHz) (/ppm). COSY-RMN (D2O) (/ppm).

(118) HSQC-RMN (D2O) (/ppm). HMBC-RMN (D2O) (/ppm).

(119) 0.05. 0.10. 0.15. 0.20. Absorbance Units. 0.25. 4000 R e l. I n t . ( % ) 100%. 3500. I:\ftir\ftir2013\atr\03\2013_08213_ARR07ABREST_atr_01.0. 250. 3000 2352.42 2324.71 2192.55 2164.70 2139.17 2051.16 1981.21 1841.81 1714.12 1634.56 1584.83 1556.38 1495.78 1481.40 1456.39 1444.68 1412.86 1384.09 1370.02 1357.57 1339.60 1320.12 1306.61 1279.69 1242.70 1213.39 1180.78 1134.93 1108.73 1085.76 1054.08 1030.02 1018.33 1003.17 979.45 949.55 934.25 904.47 864.43 815.54 787.49 765.24 720.37 709.61 634.62 589.62 573.37 554.03 539.20 487.38 470.68 425.44. 200. 2703.46. 150. 2848.54 2808.14. 0% 100. 3005.25 2958.84. 3897.93 3878.63 3861.84 3850.47 3835.09 3813.42 3742.31 3731.56 3708.28 3686.04 3667.07 3645.80 3626.25 3416.39. Espectro de masas ESI+ +TOF MS: 1.317 to 1.934 min from Sample 2 (ARR07aBREST en MeOH / H2O / CH3CN) of 2012_00415_ARR07aBREST_esitof01.wiff a=3.60108303271774060e-004, t0=-1.71509310232293010e+001 (Turbo Spray). 10%. 300 350. 2500. 2013_08213_ARR07ABREST_atr_01. 403.28 400 m/z, Da. 2000. ATR KRS-5. 450 500. 1500. Max. 4052.1 counts.. 95% 313.23. 90%. 85%. 80%. 75%. 70%. 65%. 60%. 55%. 50%. 45%. 40%. 35%. 30%. 25%. 20%. 15%. 5% 485.20. 486.21. 550 600. 1000. 650 700. Espectro IR. Wavenumber cm-1. 500. 2013/03/21.

(120) 4,11-dibencil-1,4,8,11-tetraazabiciclo[6.6.2]hexadecano (26) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).

(121) DEPT-RMN (CDCl3, 500 MHz) (/ppm). COSY-RMN (CDCl3) (/ppm).


(123) Espectro de masas ESI+ +TOF MS: 2.101 to 3.153 min from Sample 2 (ARR26BREST en MeOH / DCM / CH3CN) of 2012_00411_ARR26BREST_esitof01.wiff a=3.60117430399008280e-004, t0=-1.70049232138970790e+001 (Turbo Spray). Max. 1211.5 counts.. 407.29. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 317.26. 20% 15% 10% 5% 0% 100. 150. 200. 250. 300. 350. 400 m/z, Da. 450. 500. 550. 600. 650. 700. 1549.97 1494.25 1453.40 1394.65 1378.63 1349.13 1299.87 1267.44 1244.07 1181.07 1145.50 1123.91 1093.10 1072.89 1028.92 1006.65 973.06 914.99 889.12 839.37 815.52 759.54 738.53 724.69 703.39 620.04 570.52 542.20 491.51 440.45 410.32. 2051.80. 2835.48 2796.67. 3052.94 3023.25. 0.30 0.25 0.20 0.15 0.10 0.05. Absorbance Units. 0.35. 0.40. 0.45. 2939.14. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\04\2013_09447_arr26BREST_atr_01.0. 2013_09447_arr26BREST_atr_01. ATR KRS-5. 2013/04/02.

(124) 1,4,8,11-tetraazabiciclo[6.6.2]hexadecano – ciclam crossbridged – (27) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(127) Espectro de masas ESI+ +TOF MS: 0.900 to 1.417 min from Sample 2 (ARRcyclamCB, MeOH/ACN/DCM/CHCl3) of 2012_300890_ARRcyclamCB_esitof01.wiff a=3.60116663918206280e-004, t0=-1.66136168746710240e+001 (Turbo Spray). Max. 4130.7 counts.. 227.22. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 120. 140. 160. 180. 200. 220. 240 m/z, Da. 260. 280. 300. 320. 340. 360. 0.3 0.2 0.1. Absorbance Units. 0.4. 0.5. 1594.26 1501.51 1489.47 1455.64 1434.73 1366.53 1349.25 1318.92 1286.21 1248.48 1218.41 1167.32 1152.67 1138.97 1114.84 1094.10 1080.90 1047.25 1021.33 975.54 959.90 931.37 901.79 884.94 870.57 840.60 828.40 788.52 748.16 728.93 601.25 540.23 520.40 451.04 429.99 394.09 359.98 319.74. 2933.25 2893.89 2856.18 2820.15 2798.81 2767.14 2750.98 2680.29. 3271.77. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2012\atr\11\2012_30890_ARRtranscyclam_CB_atr01.0. 2012_30890_ARRtranscyclam_CB_atr01. Page 1/1. ATR KRS-5. 2012/11/27.

(128) Dimetil 6,6'-((1,4,8,11-tetraazabiciclo[6.6.2]hexadecano4,11-diil)bis(metilen))dipicolinato (28) 1H-RMN. 13C-RMN. (CDCl3, 500 MHz) (/ppm). (CDCl3, 125,8 MHz) (/ppm).



(131) Espectro de masas ESI+ +TOF MS: 2.402 to 3.103 min from Sample 2 (ARR30BREST en MeOH / DCM / CH3CN) of 2012_00412_ARR30BREST_esitof01.wiff a=3.60108303271774000e-004, t0=-1.71509310232293010e+001 (Turbo Spray). Max. 5084.9 counts.. 525.29. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 263.16 150. 200. 250. 300. 350. 400. 450 m/z, Da. 500. 550. 600. 650. 700. 750. 800. 1736.66. 1586.25 1438.46 1377.28 1355.23 1340.24 1321.85 1292.27 1270.55 1215.99 1193.74 1135.10 1118.69 1078.53 1065.39 1033.31 991.68 976.23 952.53 917.27 889.48 854.41 834.07 798.86 765.92 721.06 682.12 626.62 595.98 542.10 528.76 492.47 449.16 424.30. 0.25 0.20 0.15 0.10 0.05. Absorbance Units. 0.30. 0.35. 2916.54. 2837.50 2795.73. 3054.11 2997.78. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\03\2013_08212_ARR30BREST_atr_01.0. 2013_08212_ARR30BREST_atr_01. ATR KRS-5. 2013/03/21.

(132) Ácido 6,6'-((1,4,8,11-tetraazabiciclo[6.6.2]hexadecano4,11-diil)bis(metilen))dipicolínico (H2cb-tedpa·5HCl·H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz, pD = 0,9) (/ppm). (D2O, 125,8 MHz, pD = 0,9) (/ppm).






(138) Espectro de masas ESI+ +TOF MS: 3.820 to 4.738 min from Sample 2 (ARR32BREST en MeOH / H2O / CH3CN) of 2012_00434_ARR32BREST_esitof01.wiff a=3.60108303271773950e-004, t0=-1.71509310232293010e+001 (Turbo Spray). Max. 1801.5 counts.. 249.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20%. 497.27. 15% 10% 240.14 5% 108.04 135.08. 0% 100. 179.07. 150. 344.23. 227.15 218.15 200. 318.25 250. 300. 350. 400 m/z, Da. 450. 500. 550. 600. 650. 416.05. 655.86. 757.10. 835.10. 1211.44 1179.55 1152.28 1076.03 1052.57 996.60 935.42. 1455.34 1402.39 1347.69. 1614.75 1593.64. 1723.63. 1980.79. 2050.85. 2522.35. 2955.52. 0.15 0.10 0.05. Absorbance Units. 0.20. 0.25. 3333.51. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\03\2013_09113_ARR32BREST_atr_01.0. 2013_09113_ARR32BREST_atr_01. ATR KRS-5. 2013/03/25.

(139) Ácido 6,6'-((1,4,8,11-tetraazabiciclo[6.6.2]hexadecano4,11-diil)bis(metilen))dipicolínico (H2cb-tedpa·6TFA·H2O) 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(140) Espectro de masas ESI+ +TOF MS: 3.820 to 4.738 min from Sample 2 (ARR32BREST en MeOH / H2O / CH3CN) of 2012_00434_ARR32BREST_esitof01.wiff a=3.60108303271773950e-004, t0=-1.71509310232293010e+001 (Turbo Spray). Max. 1801.5 counts.. 249.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20%. 497.27. 15% 10% 240.14 5% 108.04 135.08. 0% 100. 179.07. 150. 344.23. 227.15 218.15 200. 318.25 250. 300. 350. 400 m/z, Da. 450. 500. 550. 600. 650. 416.05. 655.86. 757.10. 835.10. 1211.44 1179.55 1152.28 1076.03 1052.57 996.60 935.42. 1455.34 1402.39 1347.69. 1614.75 1593.64. 1723.63. 1980.79. 2050.85. 2522.35. 2955.52. 0.15 0.10 0.05. Absorbance Units. 0.20. 0.25. 3333.51. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\03\2013_09113_ARR32BREST_atr_01.0. 2013_09113_ARR32BREST_atr_01. ATR KRS-5. 2013/03/25.

(141)

(142) Espectros de RMN, Masas e Infrarrojo de los Complejos.

(143)

(144) [La(1,7-Medo2ampa)] 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(145) Espectro de masas ESI+ +TOF MS: 1.266 to 1.416 min from Sample 2 (ARR155) of 2013_27192_ARR155_esitof_pos_01.wiff a=3.60288067169029290e-004, t0=-1.79651964754939040e+001 R; (Turbo Spray). Max. 462.5 counts.. 574.12. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 596.10 50% 45% 40% 35% 30%. 612.07. 25% 20% 15%. 593.10. 102.13. 10% 5%. 118.12 149.03 150. 0%. 196.17. 223.07. 200. 250. 306.54315.54 353.26 300. 350. 604.09 381.30 400. 471.67 506.58 517.58 450. 500. 550 m/z, Da. 600. 652.60 650. 700. 757.24 750. 872.16879.65 800. 850. 900. 950. Espectro ESI+ HR +TOF MS: 1.266 to 1.416 min from Sample 2 (ARR155) of 2013_27192_ARR155_esitof_pos_01.wiff a=3.60288067169029290e-004, t0=-1.79651964754939040e+001 R; (Turbo Spray). Max. 462.5 counts.. 574.1161. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 575.1168 5% 0%. 574.3661 573.0. 573.5. 574.0. 574.6150 574.5. 575.0. 575.5. 576.1265 576.0 m/z, Da. 576.5. 577.0. 577.5. 578.0. 578.5.

(146) 0.0. 0.1. 0.2. 0.3. Absorbance Units. 0.4. 0.5. 4000 3500. I:\ftir\ftir2013\atr\08\2013_27192_ARR155_atr_01.0. 3000 2500. 2013_27192_ARR155_atr_01 ATR KRS-5. 2000. 1455.35 1435.43 1394.05 1379.59 1330.28 1251.94 1225.24 1203.32 1159.37 1082.50 1029.31 1015.21 968.15 935.53 906.55 807.21 781.48 718.57 679.16 637.03 573.50 515.63 496.23 434.88 385.86 349.45 332.86 323.16. 1579.42. 1981.25. 2051.06. 2324.04. 2861.27. 2988.53. 3396.02. 3850.04. Espectro IR. Wavenumber cm-1 1500 1000 500. 2013/08/13.

(147) [Eu(1,7-Medo2ampa)] 1H-RMN. (D2O, 300 MHz) (/ppm). Espectro de masas ESI+ +TOF MS: 1.349 to 1.499 min from Sample 2 (ARR143) of 2013_24498_ARR143_esitof_pos_01.wiff a=3.60121250150558340e-004, t0=-1.62056004734218070e+001 R; (Turbo Spray). Max. 422.3 counts.. 610.11. 100% 95%. 588.13. 90% 608.11 85%. 586.13. 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40%. 353.27. 35% 30% 381.30. 25%. 205.10. 20% 532.24. 15%. 554.22. 327.13. 626.09. 10% 196.17. 5% 149.02 0% 100. 227.08. 178.99 259.17. 150. 200. 250. 599.12 341.15. 313.27. 371.10. 297.08 300. 350. 400. 498.16 616.11 476.18 516.27 570.19 450. 500. 550. 600. 650.10. 711.57 782.06 722.09760.07. 650 700 m/z, Da. 750. 800. 850.25 850. 924.26 900. 950. 998.28 1000. 1072.30 1050. 1100. 1146.32 1150. 1200.

(148) +TOF MS: 1.249 to 1.499 min from Sample 2 (ARR143, MeOH) of 2014_10320_ARR143_esitof_pos_01.wiff a=3.60090363875833570e-004, t0=-1.93172181517609080e+001 R; (Turbo Spray). Max. 4045.0 counts.. 588.1308 3.8% 3.6%. 586.1324. 3.4% 3.2% 3.0% 2.8% 2.6%. R e l. In t. ( % ). 2.4% 2.2% 2.0% 1.8% 1.6% 1.4% 1.2%. 587.1360. 1.0%. 589.1334. 0.8% 0.6% 0.4% 590.1392. 0.2% 0.0%. 587.6350 586.0. 586.5. 587.0. 587.5. 588.0 m/z, Da. 588.5. 589.0. 589.5. 590.0. 590.5. 1254.11 1224.95 1202.55 1155.11 1082.71 1029.49 970.98 937.38 900.44 826.32 800.13 778.34 757.53 718.28 678.98 636.61 573.35 515.69 444.76 413.55 393.78 359.76 339.93. 1456.13 1434.22 1379.52 1325.36. 1693.64. 1588.99. 1981.44. 2164.97. 2051.46. 2324.72. 2865.31. 2990.69. 0.1. 0.2. 0.3. 0.4. 3416.75. 3850.29 3813.56. Espectro IR. 0.0. Absorbance Units. Espectro ESI+ HR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\06\2013_20331_ARR143_atr_01.0. 2013_20331_ARR143_atr_01. ATR KRS-5. 2013/06/11.

(149) [Gd(1,7-Medo2ampa)] Espectro de masas ESI+ +TOF MS: 1.266 to 1.383 min from Sample 3 (ARR153) of 2013_27190_ARR153_esitof_pos_01.wiff a=3.60290152443150970e-004, t0=-1.79579341324493060e+001 R; (Turbo Spray). Max. 202.6 counts.. 631.09. 100% 95%. 615.12. 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60%. 633.09. 55% 593.14. 50%. 612.12. 45% 40% 35%. 591.13. 102.13 30% 25%. 628.09. 20%. 353.27. 15% 440.16 456.13. 10% 5% 118.12 0%. 622.11. 369.24 164.13 196.17 259.21 150. 200. 303.20 324.04 337.57. 250. 300. 350. 381.30 400. 602.62 424.17. 515.65. 540.20. 450. 500. 550 m/z, Da. 688.59 600. 650. 700. 784.10 803.04 821.01 750. 800. 850. 906.66 900. 950. Espectro ESI+ HR +TOF MS: 1.266 to 1.383 min from Sample 3 (ARR153) of 2013_27190_ARR153_esitof_pos_01.wiff a=3.60290152443150970e-004, t0=-1.79579341324493060e+001 R; (Turbo Spray). Max. 202.6 counts.. 593.1357 48% 46% 44% 42% 40% 38% 36% 34%. 591.1344. R e l. I n t . ( % ). 32% 30% 28% 592.1363. 26%. 595.1379. 24% 22% 20% 18% 16% 590.1327. 14% 12% 10% 8% 6% 4%. 594.1432. 2% 0%. 589.1358. 587.1394 587.0. 588.0. 589.0. 590.6329 590.0. 591.0. 591.6306 592.0. 592.6335. 596.1311. 593.6484. 593.0 594.0 m/z, Da. 595.0. 596.0. 597.0. 598.0. 599.0. 600.0.

(150) 0.05. 0.10. Absorbance Units. 0.15. 4000 3500. I:\ftir\ftir2013\atr\08\2013_27190_ARR153_atr_01.0. 3000 2500. 2013_27190_ARR153_atr_01 ATR KRS-5. 2000. 1591.02 1460.63 1433.96 1380.83 1325.10 1255.45 1225.27 1203.10 1160.86 1082.98 1029.96 1003.51 970.11 938.80 900.83 846.84 826.91 804.07 776.12 757.70 718.79 679.21 638.16 573.73 516.42 473.11 442.12 415.96 373.67 361.86 342.00 328.05. 1980.99. 2051.34. 2165.04 2142.57. 2351.51 2324.59. 2865.41. 2993.55. 3898.55 3867.83 3850.57 3833.70 3813.41 3793.37 3775.88 3747.57 3720.80 3706.99 3686.38 3666.77 3645.16 3625.47 3400.65. Espectro IR. Wavenumber cm-1 1500 1000 500. 2013/08/13.

(151) [Tb(1,7-Medo2ampa)] Espectro de masas ESI+ +TOF MS: 1.133 to 1.249 min from Sample 2 (ARR144) of 2013_27189_ARR144_esitof_pos_01.wiff a=3.60289890440020730e-004, t0=-1.81333941208275180e+001 R; (Turbo Spray). Max. 536.3 counts.. 594.14. 100% 95% 90% 85% 80% 75% 532.24. 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35%. 616.12. 30% 25% 20% 15% 554.22 10% 605.13. 5% 0%. 266.63 297.57 149.02 164.13 196.17 223.07 150 200 250 300. 632.09 353.27359.27 371.10 402.20 498.18 516.26 563.18 574.18617.12 350 400 450 500 550 600 650 m/z, Da. 700. 750. 800. Espectro ESI+ HR +TOF MS: 1.133 to 1.249 min from Sample 2 (ARR144) of 2013_27189_ARR144_esitof_pos_01.wiff a=3.60289890440020730e-004, t0=-1.81333941208275180e+001 R; (Turbo Spray). Max. 536.3 counts.. 594.1360. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 595.1376. 5% 0% 593.0. 594.3784 593.5. 594.0. 594.6343 594.5. 595.0. 595.5. 596.0 m/z, Da. 596.5. 597.0. 597.5. 598.0. 598.5. 599.0.

(152) 0.05. 0.10. 0.15. Absorbance Units. 0.20. 0.25. 4000 3500. I:\ftir\ftir2013\atr\08\2013_27189_ARR144_atr_01.0. 3000. 2013_27189_ARR144_atr_01. 2500. ATR KRS-5. 2000. 1460.64 1434.47 1381.03 1323.52 1252.91 1225.39 1202.15 1156.12 1082.72 1029.48 1003.66 978.91 940.87 901.49 827.33 801.62 777.22 718.70 678.97 637.06 573.61 515.29 474.38 446.49 434.12 419.61 359.46 342.37 315.18. 1586.74. 1980.90. 2185.68 2165.52 2109.86 2051.41. 2352.17 2324.32. 2868.43. 2988.79. 3897.72 3861.25 3849.94 3834.92 3813.43 3797.88 3742.07 3731.47 3707.64 3685.69 3666.72 3625.69 3394.06. Espectro IR. Wavenumber cm-1 1500 1000 500. 2013/08/13.

(153) [Yb(1,7-Medo2ampa)] 1H-RMN. (D2O, 278K, 500 MHz) (/ppm). Espectro de masas ESI+ +TOF MS: 1.249 to 1.349 min from Sample 2 (ARR154) of 2013_24499_ARR154_esitof_pos_01.wiff a=3.60120813221048570e-004, t0=-1.62386523172546300e+001 R; (Turbo Spray). Max. 793.0 counts.. 609.15. 100% 95% 90% 85% 80%. 631.13. 75% 70%. 607.14. R e l. I n t . ( % ). 65% 60% 55% 50% 102.13 45%. 353.27. 40% 35%. 628.12. 30% 118.12 25%. 381.30. 20%. 205.10. 647.11. 15% 10% 5% 0%. 327.13 164.13 150. 313.27. 196.17. 273.19 255.15 200. 250. 300. 618.64. 360.32 341.30 413.27 350. 400. 445.12 450. 539.17 559.12 500. 550. 649.11 640.13. 600. 711.57 739.60781.08. 650 700 m/z, Da. 750. 803.07 800. 819.05 850. 924.26 900. 950. 998.28 1000. 1072.30 1050. 1100. 1147.32 1150. 1200.

(154) Espectro ESI+ HR +TOF MS: 1.266 to 1.383 min from Sample 2 (ARR154) of 2013_27191_ARR154_esitof_pos_01.wiff a=3.60286863846503690e-004, t0=-1.83530509307747710e+001 R; (Turbo Spray). Max. 131.8 counts.. 609.1490 80% 75% 70% 65% 60%. R e l. In t. ( % ). 55% 50% 45% 607.1459. 40% 35%. 608.1481 30% 25% 20% 15%. 606.1459 611.1495. 10% 610.1519. 5% 0%. 605.1470. 603.1178 603.0. 604.0. 605.0. 606.6329 606.0. 607.0. 607.6401. 608.6565. 608.0. 609.6349. 609.0. 611.2667 612.1238. 610.0 m/z, Da. 611.0. 612.0. 613.1549 613.0. 614.0. 615.1171. 616.1090. 615.0. 616.0. 617.0. 1591.86 1504.64 1434.66 1382.83 1317.68 1254.48 1225.29 1202.67 1158.19 1083.19 1029.67 1004.66 971.38 943.56 906.68 830.98 804.66 775.52 759.83 719.72 679.43 665.29 637.92 594.43 573.39 515.25 456.96 434.91 418.02 371.98 350.16 340.63 321.81. 2163.43. 2079.12 2050.37 1981.46. 2351.98 2324.77. 2232.43. 2995.98. 2872.22. 0.10 0.05. Absorbance Units. 0.15. 0.20. 3914.80 3898.07 3850.41 3835.21 3813.25 3798.25 3742.29 3731.63 3720.53 3707.99 3685.67 3667.32 3645.82 3626.01 3387.36. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\08\2013_27191_ARR154_atr_01.0. 2013_27191_ARR154_atr_01. ATR KRS-5. 2013/08/13.

(155) [Lu(1,7-Medo2ampa)] 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(156) DEPT-RMN (D2O) (/ppm). Espectro de masas ESI+ +TOF MS: 1.283 to 1.383 min from Sample 2 (ARR156) of 2013_27193_ARR156_esitof_pos_01.wiff a=3.60287004449541850e-004, t0=-1.79564076620753350e+001 R; (Turbo Spray). Max. 575.1 counts.. 610.15. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50%. 648.11. 45% 40%. 632.13. 35% 30% 25% 20% 15% 10%. 552.14. 5% 118.12 0%. 164.12 223.05 150 200. 273.18 250. 324.56333.56 353.26 300. 350. 629.13 621.14. 396.22 400. 490.20 522.16574.13 450. 500 550 m/z, Da. 600. 640.12. 650. 835.99 700. 750. 800. 850. 900.

(157) Espectro ESI+ HR +TOF MS: 1.283 to 1.383 min from Sample 2 (ARR156) of 2013_27193_ARR156_esitof_pos_01.wiff a=3.60287004449541850e-004, t0=-1.79564076620753350e+001 R; (Turbo Spray). Max. 575.1 counts.. 610.1506. 100% 95% 90% 85% 80% 75% 70%. R e l. In t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10%. 611.1522. 5% 0%. 610.4229 610.6426 608.0. 608.5. 609.0. 609.5. 610.0. 610.5. 611.0. 612.1460 611.5. 612.0. 612.5 613.0 m/z, Da. 613.5. 614.1186 614.0 614.5. 615.0. 615.5. 616.0. 616.5. 617.0. 617.5. 1591.16. 1434.92 1382.75 1319.14 1252.28 1225.83 1203.21 1156.67 1083.53 1029.72 972.54 943.68 908.25 831.72 805.19 775.92 760.26 719.39 679.47 637.02 597.30 573.77 514.67 417.26 384.92 368.42 349.51 341.02 318.64 306.36. 1981.93. 2166.45. 2051.43. 2324.41. 2990.00. 2873.18. 3380.46. 3685.72. 0.25 0.20 0.15 0.10 0.05. Absorbance Units. 0.30. 0.35. 0.40. 3850.45. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2013\atr\08\2013_27193_ARR156_atr_01.0. 2013_27193_ARR156_atr_01. ATR KRS-5. 2013/08/13.

(158) [La(dodpa)]Cl 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(159) COSY-RMN (D2O) (/ppm). HSQC-RMN (D2O) (ppm).

(160) Espectro de masas ESI+ +TOF MS: 1.818 to 2.352 min from Sample 2 (ARRLHLa en MeOH / CH3CN) of 2010_32638_ARRLHLa_esitof01.wiff a=3.59914268740018650e-004, t0=-1.32766185078181300e+001 R; (Turbo Spray). Max. 1781.2 counts.. 579.12. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 886.16. 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 1193.21 150. 200. 250. 300. 350. 400. 450. 500. 550. 600. 650 700 m/z, Da. 750. 800. 850. 900. 950. 1000. 1050. 1100. 1150. 1200. 1250. Espectro ESI+ HR +TOF MS: 5.489 to 6.991 min from Sample 3 (calibrante, agimix) of 2010_32638_ARRLHLa_esitof01.wiff a=3.59914268740018380e-004, t0=-1.32766185078181400e+001 (Turbo Spray). Max. 1076.4 counts.. 579.1226. 749 700 650 600 550. In te n s ity , c o u n ts. 500 450 400 350 300 250 200 150 100 50 0 578.6. 580.1280 578.8. 579.0. 579.2. 579.4. 579.6. 579.8. 580.0. 580.2. 580.4 m/z, Da. 580.6. 580.8. 581.0. 581.2. 581.4. 581.6. 581.8. 582.0.

(161) 0.00. 0.05. 0.10. 0.15. 0.20. 0.25. 4000 3500. I:\ftir\ftir2011\atr\02\2011_03333_ARRLHLa_atr01.0. 3000 2500. 2011_03333_ARRLHLa_atr01 ATR KRS-5. Page 1/1. 2050.50 1627.60 1582.88 1487.02 1465.61 1443.48 1432.07 1402.81 1369.43 1322.79 1264.77 1221.44 1183.13 1158.16 1133.56 1093.93 1073.12 1029.58 1012.39 982.24 946.82 911.48 875.15 847.84 812.48 796.84 778.18 767.96 717.56 680.15 638.94 593.68 547.98 497.85 450.04 426.35 411.30 382.16 350.23 336.24 317.21. 2324.79. 2866.84. 2992.57. 3340.22. Espectro IR. Wavenumber cm-1 2000 1500 1000 500. 2011/02/11.

(162) [Eu(dodpa)]Cl 1H-RMN. (D2O, 300 MHz) (/ppm). Espectro de masas ESI+ +TOF MS: 3.954 to 4.688 min from Sample 2 (ARRLHEu en MeOH / CH3CN) of 2010_32637_ARRLHEu_esitof01.wiff a=3.59915237621757870e-004, t0=-1.33678062217496090e+001 R; (Turbo Spray). Max. 1635.1 counts.. 593.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 150. 200. 250. 300. 350. 400. 450. 500 m/z, Da. 550. 600. 650. 700. 750. 800. 850. 900.

(163) +TOF MS: 5.973 to 6.641 min from Sample 3 (calibrante, agimix) of 2010_32637_ARRLHEu_esitof01.wiff a=3.59915237621757870e-004, t0=-1.33678062217496140e+001 R; (Turbo Spray). Max. 2489.2 counts.. 593.1371 1150 1100 1050 1000 950 900. 591.1357. 850. In te n s ity , c o u n ts. 800 750 700 650 600 550 500 450 400 350 300 250 200 150 100 50 0 590.5. 594.1427. 592.1417 591.0. 591.5. 592.0. 592.5. 593.0. 593.5. 594.0. 594.5. 595.0. 595.5. 596.0. m/z, Da. 2050.86 1631.57 1587.83 1490.41 1469.35 1444.38 1433.36 1406.49 1370.43 1314.95 1266.82 1221.82 1201.31 1185.48 1157.76 1135.03 1094.49 1077.18 1056.13 1032.27 1013.14 986.62 964.18 915.15 880.92 851.21 818.40 798.56 771.02 718.45 681.25 653.70 640.77 599.43 549.99 501.34 457.17 417.25 390.77 354.49 340.67. 2323.88. 2966.74. 2869.47. 0.05. 0.10. 0.15. 0.20. 0.25. 3280.60. Espectro IR. 0.00. Absorbance Units. Espectro ESI+ HR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2011\atr\02\2011_03335_ARRLHEu_atr01.0. 2011_03335_ARRLHEu_atr01. ATR KRS-5. Page 1/1. 2011/02/11.

(164) [Gd(dodpa)]Cl Espectro de masas ESI+ +TOF MS: 1.467 to 1.667 min from Sample 3 (ARRGdL1) of 2010_22387_ARRGdL1_esitof_pos.wiff a=3.59904784970231420e-004, t0=-1.27029514660345090e+001 (Turbo Spray). Max. 972.9 counts.. 598.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65%. 596.14. 60% 55% 50% 45% 40% 35% 236.14 30% 25% 20% 15% 10% 5%. 193.10. 102.13. 0% 100. 150. 310.66. 227.63. 214.62 200. 320.23. 262.15 250. 300. 385.19. 350. 412.15471.27. 400. 450. 500. 550 600 m/z, Da. 650. 700. 750. 800. 850. 900. 950. 1000. Espectro ESI+ HR +TOF MS: 1.300 to 1.517 min from Sample 2 (ARR-GdL1 en MeOH/DCM/ACN) of 2010_24423_ARR-GdL1_esitofhr03.wiff a=3.59898127081193760e-004, t0=-1.40476112181204370e+001 R; (Turbo Spray). Max. 1839.1 counts.. 598.1411. 100% 95% 90% 85% 80% 75%. 596.1404. 70%. R e l. In t. ( % ). 65% 600.1442. 60% 597.1426. 55% 50% 45% 40% 35% 595.1426. 30% 25% 20% 15% 10%. 599.1496. 5% 0%. 601.1537 594.1480 592.0. 592.5. 593.0. 593.5. 594.0. 594.5. 595.0. 595.5. 596.4474 596.0 596.5 597.0. 597.5 m/z, Da. 598.4394 598.0 598.5. 599.0. 599.5. 600.0. 600.5. 601.0. 601.5. 602.0. 602.5. 603.0.

(165) 0.00. 0.05. 0.10. 0.15. 0.20. Absorbance Units. 0.25. 0.30. 0.35. 4000 3500. I:\ftir\ftir2011\atr\02\2011_03338_ARRLHGd_atr01.0. 3000 2500. 2011_03338_ARRLHGd_atr01. 2000. ATR KRS-5. Page 1/1 1500 1000. 416.51 381.24 342.71. 1266.00 1226.21 1197.83 1156.98 1076.68 1016.23 993.59 963.97 949.45 849.84 804.60 767.43 719.50 681.12 622.13 593.03 546.88 514.21. 1437.79 1395.61 1360.84. 1642.11 1584.90. 1714.19. 2051.10. 2864.81. 3213.45. 3391.61. Espectro IR. Wavenumber cm-1 500. 2011/02/11.

(166) [Tb(dodpa)]Cl Espectro de masas ESI+ +TOF MS: 1.601 to 2.552 min from Sample 2 (ARRLHTb en MeOH / CH3CN) of 2010_33123_ARRLHTb_esitof01.wiff a=3.59915761076374430e-004, t0=-1.34618128585667570e+001 R; (Turbo Spray). Max. 4567.0 counts.. 599.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0% 100. 150. 200. 250. 300. 350. 400. 450. 500. 550 m/z, Da. 600. 650. 700. 750. 800. 850. 900. 950. 1000. Espectro ESI+ HR +TOF MS: 1.217 to 1.801 min from Sample 3 (calibrante, agimix) of 2010_33123_ARRLHTb_esitof01.wiff a=3.59915761076374430e-004, t0=-1.34618128585667570e+001 R; (Turbo Spray). Max. 1129.6 counts.. 599.1420 320 300 280 260 240. In te n s ity , c o u n ts. 220 200 180 160 140 120 100 80 60 40 20 0. 600.1468 598.8. 599.0. 599.2. 599.4. 599.6. 599.8. 600.0. 600.2 600.4 m/z, Da. 600.6. 600.8. 601.0. 601.2. 601.4. 601.6. 601.8.

(167) 0.00. 0.05. 0.10. 0.15. 0.20. Absorbance Units. 0.25. 0.30. 0.35. 4000 3500. I:\ftir\ftir2011\atr\02\2011_03336_ARRLHTu_atr01.0. 3000. 2011_03336_ARRLHTu_atr01. 2050.63 1653.10 1638.04 1593.50 1570.20 1462.28 1432.08 1373.06 1344.55 1291.16 1265.02 1252.31 1219.68 1185.80 1148.23 1130.38 1097.57 1080.19 1068.77 1056.94 1036.79 1020.73 1001.08 988.54 961.16 943.76 909.06 886.24 850.79 833.13 806.19 788.24 776.62 716.02 684.39 641.94 610.23 589.65 546.76 503.98 458.99 421.73 412.61 389.78 336.42. 2323.92. 2921.27 2867.71. 3137.48 3086.83. 3658.99. Espectro IR. 2500 Wavenumber cm-1 2000. ATR KRS-5. Page 1/1 1500 1000 500. 2011/02/11.

(168) [Yb(dodpa)]Cl 1H-RMN. (D2O, 300 MHz) (/ppm). Espectro de masas ESI+ +TOF MS: 0.482 to 0.850 min from Sample 4 (ARRLHYb en MeOH / CH3CN) of 2010_33122_ARRLHYb_esitof01.wiff a=3.59915148740154240e-004, t0=-1.35589794273567480e+001 R; (Turbo Spray). Max. 3050.1 counts.. 614.15. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 616.16. 10% 5% 0% 100. 150. 200. 250. 300. 350. 400. 450. 500. 550 m/z, Da. 600. 650. 700. 750. 800. 850. 900. 950. 1000.

(169) Espectro ESI+ HR +TOF MS: 2.635 to 3.370 min from Sample 5 (calibrante, agimix) of 2010_33122_ARRLHYb_esitof01.wiff a=3.59915148740154020e-004, t0=-1.35589794273567500e+001 (Turbo Spray). Max. 2701.3 counts.. 614.1564 420 400 380 360 340 320 300. In te n s ity , c o u n ts. 280 260 240 220 200 612.1548. 180 160 140. 613.1569 120 100 80 60. 611.1549 616.1609. 40 20 0. 615.1618 610.0. 610.5. 611.0. 611.5. 612.0. 612.5. 613.0. 613.5 m/z, Da. 614.0. 614.5. 615.0. 615.5. 616.0. 616.5. 617.0. 2051.08. 1649.71 1641.71 1597.04 1573.67 1497.13 1467.30 1451.65 1350.21 1295.57 1260.15 1221.65 1184.17 1149.52 1088.36 1071.74 1040.19 1022.17 990.92 971.68 946.84 919.96 888.75 858.01 843.77 806.24 776.96 716.54 681.25 646.47 624.59 531.96 507.09 485.49 435.61 416.09 395.68 362.98 330.71. 2249.73. 2866.89. 3049.75 2991.20. 0.25 0.20 0.15 0.10 0.05 0.00. Absorbance Units. 0.30. 0.35. 3382.40. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2011\atr\02\2011_03337_ARRLHYb_atr01.0. 2011_03337_ARRLHYb_atr01. ATR KRS-5. Page 1/1. 2011/02/11.

(170) [Lu(dodpa)]Cl 1H-RMN. 13C-RMN. (D2O, 500 MHz) (/ppm). (D2O, 125,8 MHz) (/ppm).

(171) COSY-RMN (D2O) (/ppm). HSQC-RMN (D2O) (ppm).

(172) HMBC-RMN (D2O) (ppm). Espectro de masas ESI+ +TOF MS: 1.651 to 2.268 min from Sample 2 (ARRLHLu en MeOH / CH3CN) of 2010_33124_ARRLHLu_esitof01.wiff a=3.59915069711157190e-004, t0=-1.35169541182539240e+001 R; (Turbo Spray). Max. 2579.5 counts.. 615.14. 100% 95% 90% 85% 80% 75% 70%. R e l. I n t . ( % ). 65% 60% 55% 50% 45% 40% 35% 30% 25% 20% 15% 10% 5% 0%. 150. 200. 250. 300. 350. 400. 450. 500. 550 600 m/z, Da. 650. 700. 750. 800. 850. 900. 950. 1000.

(173) Espectro ESI+ HR +TOF MS: 1.300 to 2.001 min from Sample 3 (calibrante, agimix) of 2010_33124_ARRLHLu_esitof01.wiff a=3.59915069711157240e-004, t0=-1.35169541182539220e+001 R; (Turbo Spray). Max. 824.6 counts.. 615.1576. 825 800 750 700 650 600. In te n s ity , c o u n ts. 550 500 450 400 350 300 250 200 150 100 50 0. 616.1627 614.8. 615.0. 615.2. 615.4. 615.6. 615.8. 616.0. 616.2 m/z, Da. 616.4. 616.6. 616.8. 617.0. 617.2. 617.4. 617.6. 2051.03 1654.27 1632.84 1595.28 1572.29 1464.63 1373.98 1356.40 1345.52 1292.35 1266.29 1254.00 1220.87 1187.69 1148.08 1133.18 1099.12 1081.31 1069.76 1058.55 1039.98 1022.56 1003.55 991.08 967.56 945.64 915.83 891.50 851.91 836.46 807.32 778.37 716.98 685.06 641.33 613.55 593.45 549.30 502.84 464.35 418.28 395.79 339.50 309.13. 2325.25. 2944.65. 2872.73. 3131.25 3086.80. 0.20 0.15 0.10 0.05 0.00. Absorbance Units. 0.25. 0.30. 0.35. 3368.91. Espectro IR. 4000. 3500. 3000. 2500. 2000. 1500. 1000. 500. Wavenumber cm-1. I:\ftir\ftir2011\atr\02\2011_03334_ARRLHLu_atr01.0. 2011_03334_ARRLHLu_atr01. ATR KRS-5. Page 1/1. 2011/02/11.