ELECTRONIC SUPPORTING INFORMATION Flexible Lanthanide MOFs as Highly Selective and Reusable Liquid MeOH Sorbents

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1 This journal is The Royal Society of Chemistry 3 ELECTRONIC SUPPORTING INFORMATION Flexible Lanthanide MOFs as Highly Selective and Reusable Liquid MeOH Sorbents Constantinos G. Efthymiou, a Eleni J. Kyprianidou, a Constantinos J. Milios, b Manolis J. Manos* c and Anastasios J. Tasiopoulos* a a Department of Chemistry, University of Cyprus, Nicosia, Cyprus, 678. Fax: ; Tel: ; atasio@ucy.ac.cy b Department of Chemistry, University of Crete, Voutes 73, Heracleion, Greece; c Department of Chemistry, University of Ioannina, 45 Ioannina, Greece; emanos@cc.uoi.gr

2 This journal is The Royal Society of Chemistry 3 Table S. Selected crystal data for UCY-4 UCY-8, UCY-5/MeOH and UCY-5/acetone Compound UCY-4 UCY-5 UCY-5/MeOH UCY-5/acetone UCY-6 UCY-7 UCY-8 Chemical formula C 22H LaN 3O 8 C 22H CeN 3O 8 C 69H 47Ce 4N 4O 32 C 9H 4CeNO 9 C 22H N 3O 8Pr C 4H 34N 5O 6Sm 2 C 9H 4EuN 2O 8 Formula Mass Crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic a/å 29.74(2) 29.49(2) (4) (2) (2) 28.88(2) (2) b/å (5) (6) 4.9(2) 4.299(5) 4.345(9) 4.34(7) 2.699(2) c/å 3.595(5) 3.597(7) 2.3(2) 2.834(9) 3.635(2) 3.555(6) 4.26(2) β/.97(5).9(5) 6.27(2) 24.37(9) (9) (4) (8) Unit cell volume/å (4) (4) 4929(2) 54.(7) (8) 557.(4) (9) Temperature/K (2) (2) (2) (2) (2) (2) (2) Space group C2/c C2/c C2/c C2/c C2/c C2/c C2/c No. of formula units per unit cell, Z Radiation type MoKα MoKα CuKα MoKα MoKα MoKα CuKα Absorption coefficient, μ/mm No. of reflections measured No. of independent reflections R int Final R values (I > 2σ(I)) a Final wr(f 2 ) values (I > 2σ(I)) b Final R values (all data) a Final wr(f 2 ) values (all data) b Goodness of fit on F a R =Σ Fο - Fc /Σ Fο. b wr(f 2 )=[Σ[w(F 2 o F 2 c )2]/Σ[wF 2 o )2]] /2, w=/[σ 2 (F 2 o ) + (m p) 2 + n p], p=[max(f 2 o,) + 2F 2 c ]/3, and m and n are constants 2

3 This journal is The Royal Society of Chemistry 3 Table S2. Selected crystal data for compounds UCY-9 UCY-2 Compound UCY-9 UCY- UCY- UCY-2 Chemical formula C 82H 68Gd 4N O 32 C 9H 4N 2O 8Tb C 9H 4DyN 2O 8 C 82H 68Ho 4N O 32 Formula Mass Crystal system Monoclinic Monoclinic Monoclinic Monoclinic a/å (2) 29.57(2) (8) (2) b/å 4.448(2) 3.9(2) 3.977(7) 4.354(7) c/å (8) (9) 3.693(5) 3.347(2) α/ β/ 99.76(7) (6) 99.74(3) 99.65(6) γ/ Unit cell volume/å (6) 5279.(7) 538.9(4) 545.8(6) Temperature/K (2) (2) (2) (2) Space group C2/c C2/c C2/c C2/c No. of formula units per unit cell, Z Radiation type CuKα MoKα MoKα MoKα Absorption coefficient, μ/mm No. of reflections measured No. of independent reflections R int Final R values (I > 2σ(I)) Final wr(f 2 ) values (I > 2σ(I)) Final R values (all data) Final wr(f 2 ) values (all data) Goodness of fit on F a R =Σ Fο - Fc /Σ Fο. b wr(f 2 )=[Σ[w(F 2 o F 2 c )2]/Σ[wF 2 o )2]] /2, w=/[σ 2 (F 2 o ) + (m p) 2 + n p], p=[max(f 2 o,) + 2F 2 c ]/3, and m and n are constants 3

4 This journal is The Royal Society of Chemistry 3 Fig. S Experimental and calculated PXRD patterns of UCY-2, UCY-4-UCY-2. Fig. S2 Representation of the flu-3,6-c2/c topology of UCY-2, UCY-4-UCY-2.. Pink and blue spheres represent the 6-c and 3-c nodes, respectively. 4

5 c-axis(å) a-axis(å) b-axis(å) This journal is The Royal Society of Chemistry 3 Fig. S3 Representation of the pore network of UCY La Ce Nd Pr Sm Eu Gd Tb Dy ionic radius(pm) Ho La Ce Pr Nd Sm Eu Gd Tb Dy ionic radius(pm) Ho Eu Tb PrNd Dy Sm La Ce Gd Ho ionic radius(pm) V(Å 3 ) La Ce Pr Nd Sm Eu Gd Dy Tb Ho ionic radius(pm) Fig. S4 Plots of the cell parameters of UCY-4 (La), UCY-5 (Ce), UCY-6 (Pr), UCY-2 (Nd), UCY-7 (Sm), UCY-8 (Eu), UCY-9 (Gd), UCY- (Tb), UCY- (Dy) and UCY-2 (Ho) vs. the lanthanide ionic radii. 5

6 weight loss (%) This journal is The Royal Society of Chemistry 3 Thermal Stability data 8 UCY Fig. S5 The TG (red)/ (dashed line) curves for compound UCY-4. UCY-4: The initial losses occurring from C are due to the elimination of 4 H 2 O and 4 DMF molecules (calculated loss = 28.9%; found = 28.8%). The following weight losses (47.5 %), which end at ~ 76 C, are attributed to the release of the CIP ligands (calculated loss: 49.%). 6

7 weight loss (%) weight loss (%) This journal is The Royal Society of Chemistry 3 8 UCY Fig. S6 The TG (red)/ (dashed line) curves for compound UCY-5. UCY-5: The initial losses occurring from 3-25 C are assigned to the removal of 6 H 2 O and 4 DMF molecules (calculated loss = 3.8 %; found = 3.9 %). The following weight losses (45.6 %), which end at ~ 456 C, are due to the release of the CIP ligands (calculated loss: 47.7 %). 8 UCY Fig. S7 The TG (red)/ (dashed line) curves for compound UCY-6. 7

8 weight loss (%) This journal is The Royal Society of Chemistry 3 UCY-6: The initial losses occur from C and are ascribed to the elimination of 5.5 H 2 O and 4 DMF molecules (calculated loss = 3.2%; found = 3.3%). The following weight losses (46.%), which end at ~ 58 C, are due to the release of the CIP ligands (calculated loss: 48. %). 8 UCY Fig. S8 The TG (red)/ (dashed line) curves for compound UCY-7. UCY-7: The initial losses occurring from 3-24 C are due to the elimination of 4 H 2 O and 3 DMF molecules (calculated loss = 24. %; found = 24. %). The following weight losses (5.4 %), which end at ~ 65 C, are attributed to the release of the CIP ligands (calculated loss: 5.2 %). 8

9 weight loss (%) weight loss (%) This journal is The Royal Society of Chemistry 3 8 UCY Fig. S9 The TG (red)/ (dashed line) curves for compound UCY-8. UCY-8: The initial losses occurring from 3-3 C are due to the elimination of 6.5 H 2 O and 4 DMF molecules (calculated loss = 3.9 %; found = 3.7 %). The following weight losses (44.4 %), which end at ~ 653 C, are attributed to the release of the CIP ligands (calculated loss: 46.5 %). 8 UCY Fig. S The TG (red)/ (dashed line) curves for compound UCY-9. UCY-9: The initial losses occurring from C are due to the elimination of 5.5 H 2 O and 4 DMF molecules (calculated loss = 29.5 %; found = 29.2 %). The following weight losses (46. 9

10 weight loss (%) weight loss (%) This journal is The Royal Society of Chemistry 3 %), which end at ~ 65 C, are attributed to the release of the CIP ligands (calculated loss: 46.5 %). 8 UCY Fig. S The TG (red)/ (dashed line) curves for compound UCY-. UCY-: The initial losses occurring from 3-24 C are due to the elimination of 7.5 H 2 O and 2 DMF molecules (calculated loss = 23. %; found = 23. %). The following weight losses (49.4 %), which end at ~ 6 C, are attributed to the release of the CIP ligands (calculated loss: 5.9 %). 8 UCY Fig. S2 The TG (red)/ (dashed line) curves for compound UCY-.

11 weight loss (%) This journal is The Royal Society of Chemistry 3 UCY-: The initial losses occurring from C are due to the elimination of 6H 2 O and 3DMF molecules (calculated loss = 25.7 %; found = 25.9 %). The following weight losses (47.7 %), which end at ~ 647 C, are attributed to the release of the CIP ligands (calculated loss: 48.8 %). 8 UCY Fig. S3 The TG (red)/ (dashed line) curves for compound UCY-2. UCY-2: The initial losses occurring from C are due to the elimination of 8 H 2 O and 4 DMF molecules (calculated loss = 3,7 %; found = 3.5 %). The following weight losses (43.7 %), which end at ~ 64 C, are attributed to the release of the CIP ligands (calculated loss: 44.7 %).

12 This journal is The Royal Society of Chemistry 3 MeOH adsorption data A. Data for the calculation of the sorption isotherm MeOH 7 min Toluene MeOH 7 min Toluene.4 x.5.5 x.8.34 x2.3 x.47 x x3 x Fig. S4 H-NMR spectra in CD 3 Cl of the supernatant liquids resulted from the reactions of UCY-5/dry with MeOH in various molar ratios (various equivalents of MeOH per mol of UCY- 5/dry) for an adsorption time of ~2 h. The numbers under each peak represent the values of the peak integrals. In the initial solutions used (i.e. before the sorption process) the ratio of peak integrals was equal to. The exact quantities of the reactants in the various reactions performed are: x.5 [MeOH (4.5 μl,3.56 mg,. mmol,.5 eq.), toluene (.75 μl,.25 mg,. mmol ), UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl], x.8 [MeOH (7.2 μl, 5.69 mg,.78 mmol,.8 eq.), toluene (8.8 μl,6.4 mg,.78 mmol) and UCY-5/dry (. g,.222mmol) in 4mL CD 3 Cl], x [MeOH (9 μl, 7. mg,.222 mmol, eq.), toluene (23. 5 μl,.5mg,.222mmol) and UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl], x2 [MeOH (8 μl,4.22mg,.444 mmol, 2 eq.), toluene (47 μl, 4. mg,.444 mmol) and UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl], x2.5 [MeOH (22.5 μl, 7.78mg,.555 mmol 2.5 eq.), toluene (58.75 μl/5.25 mg/.555 mmol), UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl], x3 [MeOH (27 μl,2.33 mg,.666 mmol, 3 2

13 Intensity(a.u.) This journal is The Royal Society of Chemistry 3 eq.), toluene (7.5 μl, 6.5 mg,.666 mmol) and UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl] and x3.5 [MeOH (3.5 μl, mg,.777 mmol, 3.5 eq.), toluene (82.25 μl, 7.75 mg,.777 mmol) and UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl]. The peaks at 2.35 and 3.49 correspond to the methyl groups of toluene and MeOH respectively. The concentrations of MeOH after the sorption processes were determined using as reference the toluene that is not absorbed by UCY-5/dry at these reaction conditions (i.e magnetic stirring at room temperature and atmospheric pressure) and thus its concentration remains unchanged after the treatment of the solution with UCY-5/dry. For each experiment, the initial concentrations of MeOH and toluene were equal (i.e. the ratio of the peak integrals for the methyl groups of toluene and MeOH were equal to in the H-NMR spectra of the initial solutions). B. PXRD studies UCY-5/MeOH UCY-5/acetone UCY-5/dry UCY-5(pristine) ( ) Fig. S5 PXRD patterns of UCY-5 (pristine), UCY-5/dry, UCY-5/acetone and UCY- 5/MeOH. 3

14 Intensity(a.u.) This journal is The Royal Society of Chemistry 3 UCY-5/MeOH(2 nd cycle) UCY-5/MeOH( st cycle) UCY-5/acetone(2 nd cycle) UCY-5/acetone( st cycle) Fig. S6 PXRD patterns of UCY-5/MeOH prepared from original UCY-5/dry (UCY- 5/MeOH st cycle), UCY-5/MeOH prepared from regenerated UCY-5/dry (UCY- 5/MeOH 2 nd cycle), UCY-5/acetone prepared from original UCY-5/dry (UCY-5/acetone st cycle) and UCY-5/acetone prepared from regenerated UCY-5/dry (UCY-5/acetone 2 nd cycle). 4

15 This journal is The Royal Society of Chemistry 3 C. Kinetic experiments MeOH Toluene MeOH Toluene min.3 7 min.35 min.4 44 min.27 3 min min 6 min min Fig. S7 H-NMR spectra in CD 3 Cl of aliquots taken at various adsorption times from suspensions containing equimolar initial amounts of MeOH (9 μl/7. mg/.222 mmol, eq.), toluene (23. 5 μl,.5mg,.222mmol) and UCY-5/dry (. g,.222 mmol) in CD 3 Cl (4mL). The numbers under each peak represent the values of the peak integrals. MeOH Toluene MeOH Toluene.47 min 5 min min.4 8 min min 7 min min Fig. S8 H-NMR spectra in CD 3 Cl of aliquots taken at various adsorption times from suspensions containing initial amounts of MeOH (8 μl, 4.22mg,.444 mmol, 2 eq.), UCY- 5

16 This journal is The Royal Society of Chemistry 3 5/dry (. g,.222 mmol) and toluene (47 μl, 4. mg,.444 mmol) in 4mL CD 3 Cl. The numbers under each peak represent the values of the peak integrals. D. MeOH/EtOH selectivity experiments MeOH Toluene EtOH MeOH Toluene EtOH min min.5 5 min 288 min min.35 7 min min Fig. S9 H-NMR spectra in CD 3 Cl of aliquots taken at various adsorption times from suspensions containing equimolar initial amounts of MeOH (9 μl, 7. mg,.222 mmol, eq.), EtOH (2.9 μl,.2 mg,.222 mmol, eq.), toluene (23. 5 μl,.5mg,.222mmol), UCY- 5/dry (. g,.222 mmol) in 4mL CD 3 Cl. The numbers under each peak represent the values of the peak integrals. 6

17 This journal is The Royal Society of Chemistry 3 MeOH Toluene EtOH MeOH Toluene EtOH 2 min min min min min min 7 min 36 min Fig. S H-NMR spectra in CD 3 Cl of aliquots taken at various adsorption times from suspensions containing initial amounts of MeOH (9μL, 7.mg,.222mmol, eq.), EtOH (25.8 μl,.4mg,.444mmol, 2 eq.), toluene (23. 5 μl,.5mg,.222mmol) and UCY-5/dry (. g,.222 mmol) in 4mL CD 3 Cl. The numbers under each peak represent the values of the peak integrals. 7