Pillar[5]arene-based phosphine oxides: novel ionophores ... · ionophores for solvent extraction separation of f-block elements from acidic media Yuyu Fang, Lei Wu, Jiali Liao,

S1

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

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

S2

Contents

1. General Information ............................................................................. 3

2. NMR and ESI-HRMS Spectra ............................................................ 4

3. Extraction of Lanthanides and Actinides ......................................... 16


S3

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.


S4

2. NMR and ESI-HRMS Spectra

Figure S1. 1H NMR spectrum (400 MHz, CDCl3) of 4a.


S5

Figure S2. 1H NMR spectrum (400 MHz, CDCl3) of 4b.

Figure S3. 1H NMR spectrum (400 MHz, CDCl3) of 4c.


S6

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.


S7


Figure S7. 13C NMR spectrum (100 MHz, CDCl3) of 1a.


S8

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.



S9

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.


S10

Figure S12 1H NMR spectrum (400 MHz, CDCl3) of 1c.

Figure S13 13C NMR spectrum (100 MHz, CDCl3) of 1c.


S11

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]+




S12

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.


S13


Figure S19 13C NMR spectrum (400 MHz, CDCl3) of 2b.


S14

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.


S15

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



S16

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


Documents

Pillar[5]arene-based phosphine oxides: novel ionophores ... · ionophores for solvent extraction separation of f-block elements from acidic media Yuyu Fang, Lei Wu, Jiali Liao,