pillar[5]arene-based phosphine oxides: novel ionophores ... · ionophores for solvent extraction...
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Pillar[5]arene-based phosphine oxides: novel
ionophores for solvent extraction separation of
f-block elements from acidic media
Yuyu Fang, Lei Wu, Jiali Liao, Long Chen, Yuanyou Yang, Ning Liu, Lutao He, Shuliang Zou, Wen Feng,* Lihua Yuan*
Institute of Nuclear Science and Technology, Key Laboratory for Radiation Physics
and Technology of Ministry of Education, College of Chemistry, Sichuan University,
Chengdu 610064, China. Fax: +86-28-85418755; Tel: +86-28-85416996; E-mail:
[email protected]; [email protected].
Supporting Information
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Contents
1. General Information ............................................................................. 3
2. NMR and ESI-HRMS Spectra ............................................................ 4
3. Extraction of Lanthanides and Actinides ......................................... 16
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1. General Information
The 1H NMR and 13C NMR spectra were recorded on Bruker AVANCE AV II- 400
MHz (1H: 400 MHz; 13C: 100 MHz). Chemical shifts are reported in δ values in ppm
using tetramethlysilane (TMS) and coupling constants (J) are denoted in Hz.
Multiplicities are denoted as follows: s = singlet, d = doublet, t = triplet, dd = double
doublet and m = multiplet. High resolution mass (HRMS) data were obtained by
WATERS Q-TOF Premier. Solvents for extraction and chromatography were reagent
grade. CH2Cl2 was distilled from CaH2. CDCl3 were from Cambridge Isotope
Laboratories (CIL). UV- spectra were measured by SHIMADZU UV-2450. Inductive
coupled plasma atomic emission spectroscopy (ICP-AES) measurements were made
by Thermo Elemental, U.S.A.
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2. NMR and ESI-HRMS Spectra
Figure S1. 1H NMR spectrum (400 MHz, CDCl3) of 4a.
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Figure S2. 1H NMR spectrum (400 MHz, CDCl3) of 4b.
Figure S3. 1H NMR spectrum (400 MHz, CDCl3) of 4c.
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Figure S4. 13C NMR spectrum (100 MHz, CDCl3) of 4c. 31-Dec-201212:45:52
m/z2100 2120 2140 2160 2180 2200 2220 2240 2260 2280 2300 2320 2340 2360 2380 2400 2420 2440 2460 2480 2500
%
0
100
121231_4C 41 (0.705) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (8:59) TOF MS ES+ 6942264.2131
2263.2356
2262.2080
2237.05592207.1042
2108.1294
2131.0286 2206.10992168.0483
2235.19562208.1311
2234.0779
2238.0168
2262.0303
2265.1794
2291.2725
2266.1548
2290.2375
2266.2700
2292.2874
2319.3018
2473.46072322.2913 2349.2498
2348.1111 2350.3574 2447.46342376.2783
2444.55692395.2729
2475.2266
2481.3442
Figure S5. ESI-HRMS spectrum of 4c.
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Figure S6. 1H NMR spectrum (400 MHz, CDCl3) of 1a.
Figure S7. 13C NMR spectrum (100 MHz, CDCl3) of 1a.
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08-Mar-201209:49:40
m/z1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600 1650 1700 1750 1800 1850 1900 1950 2000
%
0
100
120308_FYY_PC2PO 90 (1.547) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (4:117) TOF MS ES+ 6.16e31446.9513
1446.4507
1346.9331
1346.4320
1332.9097
1116.6466
1115.99191049.9835
1332.40881117.3217
1218.8782 1318.9005
1347.4354
1347.9303
1365.9094
1366.9122
1447.4542
1447.9570
1448.4524
1457.9425
1466.4324
1466.9268
1467.43881674.4869
1479.9152 1673.4801 1942.24001675.48321882.5704 1950.9165
Figure S8. ESI-HRMS spectrum of 1a.
Figure S9. 1H NMR spectrum (400 MHz, CDCl3) of 1b.
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Figure 10. 13C NMR spectrum (100 MHz, CDCl3) of 1b.
19-Jan-201215:50:34
m/z3000 3025 3050 3075 3100 3125 3150 3175 3200 3225 3250 3275 3300 3325 3350 3375 3400 3425 3450 3475
%
0
100
120119_FYY_PC4PO 4 (0.068) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (1:58) TOF MS ES+ 1.20e33195.1982
3173.2317
3172.1863
3171.88063083.02643055.56862998.0151
3094.7112
3197.1973
3198.1799
3198.3394
3199.27473213.2080
3263.08133273.2043 3413.39163314.4136 3428.46633452.4985
Figure S11. ESI-HRMS spectrum of 1b.
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Figure S12 1H NMR spectrum (400 MHz, CDCl3) of 1c.
Figure S13 13C NMR spectrum (100 MHz, CDCl3) of 1c.
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19-Sep-201216:52:29
m/z3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 3550 3600 3650 3700 3750 3800 3850 3900 3950
%
0
100
120919_FYY_P_C6_PO 17 (0.292) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (1:59) TOF MS ES+ 4.34e33476.5120
3475.5095
3474.6118
3470.56713274.41873192.38703083.85573023.6379 3424.89893333.6292
3477.5869
3478.4722
3478.5840
3491.4565
3492.48053494.3936
3560.5671 3623.7126
[M+Na]+
Figure S14. ESI-HRMS spectrum of 1c.
Figure S15. 1H NMR spectrum (400 MHz, CDCl3) of 2a.
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Figure S16 13C NMR spectrum (400 MHz, CDCl3) of 2a. 31-Dec-201213:02:15
m/z100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100
121231_2A 10 (0.171) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (2:59) TOF MS ES+ 8.44e4589.1682
567.1852
431.1310
214.7884214.4832213.2736
134.6719215.4065
369.1830318.2980216.0084
453.1134
454.1170
470.0930 518.1285
590.1718
605.1430741.3008
606.1469
626.2545668.3075
669.3113
742.3029
883.2477840.4562
743.3072
809.7098
885.4892997.3225928.5114
Figure S17. ESI-HRMS spectrum of 2a.
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Figure S18. 1H NMR spectrum (400 MHz, CDCl3) of 2b.
Figure S19 13C NMR spectrum (400 MHz, CDCl3) of 2b.
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31-Dec-201212:59:13
m/z100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100
121231_2B 2 (0.034) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (1:58) TOF MS ES+ 9.80e4623.2484
106.0359
106.2726287.1218106.5119
285.7842188.9054369.1831
318.2964437.1407
481.1552 497.1392 605.2550
645.2302
646.2350
797.3636
661.2064
662.2095
724.3700725.3754
798.3668
799.3699940.5496896.5193
800.3696 954.3498
Figure S20. ESI-HRMS spectrum of 2b.
Figure S21. 1H NMR spectrum (400 MHz, CDCl3) of 2c.
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Figure S22 13C NMR spectrum (400 MHz, CDCl3) of 2c. 31-Dec-201213:05:39
m/z100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100
121231_2C 54 (0.923) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (2:59) TOF MS ES+ 8.02e4679.3105
511.1906
489.2051460.1565
148.6012 369.1855318.2971274.1301249.1728 447.1244
540.2183
541.2208589.1661
701.2933
702.2969
717.2701
718.2738853.4257
752.4013753.4045
854.4300
855.4301 996.6210952.5894
Figure S23. ESI-HRMS spectrum of 2c.
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3. The Extraction of Lanthanides and Actinides
Table S1 Separation factors (SF) of f-element cations for 1 and 2a (1.0×10-3 M) from 1
M HNO3 aqueous solution into dichloromethane (T = 20 ± 1°C).
Cations 1a 1b 1c 2a
DTh / DM DU / DM DTh / DM DU / DM DTh / DM DU / DM DTh / DM
La3+ 1.02 4.15 6.78 109 12.2 70.7 0.32
Ce3+ 1.14 4.65 3.83 61.6 12.0 69.5 0.31
Pr3+ 1.08 4.38 4.14 66.5 11.7 67.8 0.30
Nd3+ 1.45 5.91 3.31 53.1 11.2 65.3 0.32
Sm3+ 1.44 5.85 3.68 59.2 9.76 56.7 0.34
Eu3+ 1.47 5.98 3.38 54.3 11.4 66.1 0.32
Gd3+ 1.34 5.46 4.44 71.3 11.1 64.5 0.36
Yb3+ 1.57 6.43 3.96 63.6 16.3 94.5 0.38
Lu3+ 1.38 5.60 4.74 76.2 14.5 84 0.41
Th4+ -- 4.07 -- 16.1 -- 5.89
Table S2 Extraction percentage (%E) and separation factors (SF)of thorium(IV) and
uranyl(VI) nitrates from 1 M HNO3 and various sodium nitrate aqueous solution into
dichloromethane containing the ligand 1b (T = 20 ± 1°C).
Cations n M NaNO3 + 1 M HNO3 (n = 0-4)
0 M 1 M 2 M 3 M 4 M
Th4+ 23.6 28.7 30.7 30.7 30.7 UO2
2+ 56.0 64.1 74.0 80.7 83.0 DU / DTh 4.12 4.44 6.42 9.43 11.0
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