A. Aragón-Muriel et al. / Polyhedron xxx (2014) xxx–xxx
3
Fig. 2. Synthetic method for the preparation of La(III) complexes with cinnamate and phenylacetate ligands.
step, calc. 2 ꢂ H2O = 5.10%), 41.90% (300–600 °C, 2 steps, calc. La2-
3.48 (7), 2.85 (7). TGA mass loss 8.12% (55–120 °C, 1 step, calc.
O2CO3 formation = 44.84%).
3 ꢂ H2O = 7.70%), 49.30% (300–450 °C,
1
step, calc. La2O3
formation = 49.70%).
2.2.4. Synthesis of [La(4-Clcinn)3]ꢀ2H2O (4)
2.2.7. Synthesis of [Ce(cinn)3] (7)
The synthesis of 4 was carried out in identical manner to 1.
White powder, yield: 780 mg, 81%. C27H22Cl3LaO8, Elemental anal-
ysis; C, 44.81 (calc. 45.06); H, 2.93 (3.08); La, 19.80 (19.30)%. IR
(KBr pellet cmꢁ1): 3410 w, br, 1639 s, 1572 m, 1509 vs 1494 sh,
1423 vs 1398 s, 1285 w, 1249 m, 1092 s, 1012 m, 983 s, 828 vs
749 m, 720 m, 664 w, 554 w, 541 w, 499 m, 455 m, 266 m,
243 m. 1H NMR (DMSO-d6) d (ppm) 6.48 (d, 3H, 3J = 16.14 Hz, H-
The synthesis of 7 was carried out in identical manner to 1. Pale
yellow powder, yield: 710 mg, 91%. C27H21CeO6, Elemental analy-
sis; C, 54.54 (calc. 55.76); H, 4.03 (3.64); Ce, 24.37 (24.09)%. IR
(KBr pellet cmꢁ1): 3050 w, 1636 s, 1575 w, 1529 m, 1499 vs
1450 m, 1395 vs 1290 w, 1243 s, 982 s, 879 m, 850 m, 7709 s,
737 s, 688 m, 589 s, 540 m, 481 w. Powder XRD [d-spacings/ÅA (I/
I°)]- 11.31 (100), 6.53 (39), 5.66 (30), 5.41 (2), 4.48 (12), 4.28
(27), 3.91 (6), 3.77 (5), 3.67 (3), 3.49 (3).
20), 7.35 (d, 6H, 3J = 7.83 Hz, H-3), 7.41 (d, 3H, J = 16.14 Hz, H-10),
3
and 7.55 (d, 6H, 3J = 7.83 Hz, H-2); 13C NMR d (ppm) 125.75 (C-
20), 129.23 (C-3), 129.80 (C-2), 134.23 (C-1), 134.530 (C-4), 139.76
(C-10), and 175.07 (C@O). Powder XRD [d-spacings/ÅA (I/I°)]- 22.09
(100), 10.74 (31), 7.30 (15), 6.63 (10), 6.14 (4), 5.47 (14), 5.43
(19), 5.37 (7), 4.84 (19), 4.10 (9), 3.97 (4), 3.63 (15), 3.25 (11),
2.2.8. Synthesis of [Nd(cinn)3] (8)
The synthesis of 8 was carried out in identical manner to 1. Pale
blue powder, yield: 690 mg, 85%. C27H21NdO6, Elemental analysis;
C, 53.21 (calc. 55.37); H, 3.83 (3.61); Nd, 24.86 (24.63)%. IR (KBr
pellet cmꢁ1): 3053 w, 1636 s, 1575 m, 1530 m, 1500 vs 1450 m,
1398 vs 1290 w, 1244 s, 1201 w, 1072 w, 983 s, 879 m, 850 m,
2.72 (8). TGA mass loss 4.51% (80–125 °C,
1 step, calc.
2 ꢂ H2O = 5.01 %), 15.00% (160–320 °C,
2
steps, calc. 3 ꢂ Cl
[La(cinn)3 formation] = 15.11%), 34.20% (330–550 °C, 1 step, calc.
La2O2CO3 formation = 36.28%).
780 s, 742 s, 688 m, 589 s, 540 m, 483 m. Powder XRD [d-spac-
0
ings/AÅ (I/I°)]- 11.21 (100), 6.53 (29), 5.66 (29), 5.38 (7), 4.47 (25),
4.28 (20), 3.90 (11), 3.77 (4), 3.63 (4), 3.46 (3), 3.35 (4), 3.27 (5).
2.2.5. Synthesis of [La(4-OMephac)3]ꢀ4H2O (5)
The synthesis of 5 was carried out in identical manner to 1.
White powder, yield: 740 mg, 78%. C27H35LaO13, Elemental analy-
sis; C, 45.30 (calc. 45.90); H, 4.75 (4.99); La, 19.97 (19.66)%. IR
(KBr pellet cmꢁ1): 3221 m, br, 2959 w, 2836 w, 1557 s, 1516 s,
1431 s, 1401 s, 1283 m, 1248 s, 1179 m, 1108 w, 1034 m, 937 w,
822 m, 733 m, 697 m, 568 w, 259 m, 236 m. 1H NMR (DMSO-d6)
d (ppm) 3.26 (s, 6H, H-10), 3.71 (s, 9H, –O–CH3), 6.79 (d, 6H,
3J = 8.53 Hz, H-3), and 7.14 (d, 6H, 3J = 8.53 Hz, H-2); 13C NMR d
(ppm) 43.55 (C-10), 54.95 (–O–CH3), 113.17 (C-3), 129.21 (C-1),
2.2.9. Synthesis of [Sm(cinn)3]ꢀH2O (9)
The synthesis of 9 was carried out in identical manner to 1.
Beige powder, yield: 740 mg, 88%. C27H23SmO7, Elemental analy-
sis; C, 53.27 (calc. 53.18); H, 3.49 (3.80); Sm, 24.88 (24.66)%. IR
(KBr pellet cmꢁ1): 3422 w, br,3054 w, 1636 s, 1576 m, 1500 vs
1449 m, 1394 vs 1291 w, 1243 s, 1200 w, 1073 w, 983 s, 880 m,
850 m, 780 s, 743 s, 730 m, sh, 689 m, 589 s, 542 m, 482 m, 371
m, 335 m, 282 m, 251 m, 236 m, 227 s. Powder XRD [d-spacings/
0
ÅA (I/I°)]- 11.47 (100), 6.53 (31), 5.65 (29), 5.36 (7), 4.45 (9), 4.28
(23), 3.89 (11), 3.77 (10), 3.61 (7), 3.44 (4), 3.34 (5), 3.27 (5),
3.14 (7).
130.36 (C-2), 157.39 (C-4), 181.67 (C@O). Powder XRD [d-spac-
0
ings/AÅ (I/I°)]- 9.77 (82), 8.73 (29), 7.97 (33), 6.52 (100), 6.11 (6),
5.22 (7), 4.89 (8), 4.71 (7), 4.59 (4), 4.36 (4), 4.26 (14), 3.99 (9),
3.20 (5), 3.05 (6), 2.79 (4), 2.76 (6), 2.42 (7), 2.16 (5). TGA mass loss
10.41% (50–125 °C,
(300–530 °C, 1 step, calc. La2O3 formation = 48.63%).
1
step, calc. 4 ꢂ H2O = 10.20%), 50.06%
2.2.10. Synthesis of [Yb(cinn)3] (10)
The synthesis of 10 was carried out in identical manner to 1.
White powder, yield: 630 mg, 79%. C27H21YbO6, Elemental analy-
sis; C, 50.25 (calc. 52.77); H, 3.35 (3.44); Yb, 28.84 (28.16)%. IR
(KBr pellet cmꢁ1): 3028 w, 1636 vs 1577 s, 1518 vs 1452 vs
sh,1419 vs 1291 m, 1253 s, 1238 s, 1204 w, 1180 w, 1072 w, 985
2.2.6. Synthesis of [La(4-Clphac)3]ꢀ3H2O (6)
The synthesis of 6 was carried out in identical manner to 1.
White powder, yield: 780 mg, 83%. C24H24LaCl3O9, Elemental anal-
ysis; C, 39.19 (calc. 41.08); H, 3.32 (3.45); La, 19.48 (19.80)%. IR
(KBr pellet cmꢁ1): 3410 m, br, 2915 w, 1544 vs 1493 m, 1422 s,
1397 vs 1288 s, 1202 w, 1177 w, 1092 s, 1017 m, 934 w, 857 m,
810 s, 743 s, 685 s, 633 w, 581 m, 504 m, 469 m, 302 w, 277 w,
s, 876 s, 852 w, 779 s, 747 s, 725 m, 686 s, 592 s, 556 m, 485 m.
0
Powder XRD [d-spacings/AÅ (I/I°)]- 12.96 (100), 11.50 (31), 8.95
(22), 8.31 (25), 6.49 (57), 5.84 (8), 5.76 (6), 5.48 (14), 5.42 (4),
5.12 (6), 4.69 (4), 4.46 (8), 4.16 (6), 3.96 (19), 3.89 (5), 3.75 (4),
3.67 (6), 3.19 (5), 3.07 (6).
1
259 m, 231 w. H NMR (DMSO-d6) d (ppm) 3.32 (s, 6H, H-10),
7.21 (d, 6H, 3J = 8.78 Hz, H-3), and 7.24 (d, 6H, 3J = 8.53 Hz, H-2);
13C NMR d (ppm) 43.58 (C-10), 127.58 (C-3), 130.34 (C-1), 131.27
2.2.11. Synthesis of [Sm(4-OMephac)3]ꢀH2O (11)
0
(C-2), 136.15 (C-4), 180.80 (C@O). Powder XRD [d-spacings/AÅ (I/
I°)]- 9.40 (26), 8.96 (100), 8.32 (45), 8.09 (5), 6.48 (33), 5.97 (49),
5.04 (8), 4.94 (5), 4.70 (5), 4.61 (6), 4.48 (5), 4.05 (6), 3.68 (6),
The synthesis of 11 was carried out in identical manner to 1.
White powder, yield: 690 mg, 76%. C27H29SmO10, Elemental analy-
sis; C, 48.71 (calc. 48.85); H, 4.24 (4.40); Sm, 22.55 (22.65)%. IR