Supplementary Figure S1 A comparison between the indium trimer in ITC-n and nickel trimer in ITC-n-Ni.

Transcription

1 Supplementary Figure S1 A comparison between the indium trimer in ITC-n and nickel trimer in ITC-n-Ni.

2 Supplementary Figure S2 Powder XRD and the simulation pattern of (a) ITC-1, (b) ITC-2, ITC-2NH 2 and ITC-2Br, (c) ITC-3, (d) ITC-4, (e) ITC-2-Ni and (f) ITC-3-Ni.

3 Supplementary Figure S3 Thermogravimetric analysis (TGA) for all six as-synthesized compounds.

4 Supplementary Figure S4 A comparison of (001) projection of the topology among different ITC-n.

5 Supplementary Figure S5 Three types of pores and their space filling diagrams in ITC-n.

6 Supplementary Figure S6 Structures of guest dye molecules used in this study.

7 Supplementary Figure S7 The ion-exchange process of the three -1 charged dyes of different sizes (TOO -, AR88 -, AO7 - ) with ITC-4 as the host, showing gradual decrease in the concentration due to the removal from the solution by the ion exchange with NO 3 - in ITC-4. Note that residual dye concentrations after 60 hours show that the ion-exchange is incomplete for -1 charged dyes.

8 Supplementary Figure S8 UV-vis absorbance of (a) Sudan I (SDI 0 ), (b) Acid Orange 7 (AO7 - ), (c) Acid Red 88 (AR88 - ) and (d) Tropaeolin OO (TOO - ) at different time during ion-exchange process with ITC-4 as the host, showing the absence of ion exchange for neutral SDI and gradual decrease in the concentration due to the removal from the solution by the ion exchange with NO 3 - in ITC-4 for the later three -1 charged dyes.

9 Supplementary Figure S9 UV-vis absorbance of a set of -2 charged dyes of different size at different time during ion-exchange process with ITC-4 as the host, showing gradual decrease in the concentration due to the removal from the solution by the ion exchange with NO 3 - in ITC-4 for (a) Orange G (OG 2- ), (b) Crystal Ponceau 6R (P6R 2- ), (c) Croscein Scarlet 3B (CS3B 2- ), (d) Croscein Scarlet 7B (CS7B 2- ) and (e) Acid Blue 1 (AB1 2- ), but no change in the concentration due to size selectivity for (f) Methyl Blue (MB 2- ).

10 Supplementary Figure S10 UV-vis absorbance of the -3 charged dye New Coccine (NC 3- ) at different time during ion-exchange process with ITC-4 as the host, showing gradual decrease in the concentration due to the removal from the solution by the ion exchange with NO 3 - in ITC-4.

11 Supplementary Figure S11 UV-vis absorbance of Orange G (OG 2- ) at different time during ion-exchange process with ITC-n host with different pore size and charge, showing the absence of ion exchange due to the window size exclusion for (a) ITC-1, charge exclusion for (b) ITC-2Ni and (c) ITC-3Ni and gradual decrease of OG 2- concentration due to the removal from the solution by the ion exchange with NO 3 - in (d) ITC-2, (e) ITC-2Br, (f) ITC-2NH2, (g) ITC-3, (h) ITC-4.

12 Supplementary Figure S12 UV-vis absorbance of Orange G (OG 2- ) at different time after the addition of 1 mmol NaNO 3 during release experiments. The release of Orange G from the pores of ICT-4 due to ion exchange with NO 3 - increases the concentration of OG 2- in the solution as shown by UV-Vis absorption.

13 Supplementary Figure S13 ORTEP drawing of a fragment in ITC-1. Thermal ellipsoids are displayed with 50% probability.

14 Supplementary Figure S14 ORTEP drawing of a fragment in ITC-2. Thermal ellipsoids are displayed with 50% probability.

15 Supplementary Figure S15 ORTEP drawing of a fragment in ITC-2NH 2. Thermal ellipsoids are displayed with 50% probability.

16 Supplementary Figure S16 ORTEP drawing of a fragment in ITC-3. Thermal ellipsoids are displayed with 50% probability.

17 Supplementary Figure S17 ORTEP drawing of a fragment in ITC-4. Thermal ellipsoids are displayed with 50% probability.

18 Supplementary Table S1 A summary of crystallography data for ITC-n. Detailed data are given in Supplementary Tables S3-S7. Code Formula Sp. Gr. a (Å) c (Å) V (Å 3 ) R Mw (g/mol) ITC-1 [In 3O(ina) 3(bdc) 1.5](NO 3) I-43m (5) (5) (4) ITC-2 [In 3O(pba) 3(bdc) 1.5](NO 3) I-43m (16) (16) 21388(2) ITC-2NH 2 [In 3O(pba) 3(NH 2-bdc) 1.5](NO 3) I-43m (6) (6) (8) ITC-2Br [In 3O(pba) 3(Br-bdc) 1.5](NO 3) I-43m N/A ITC-3 [In 3O(pba) 3(ndc) 1.5](NO 3) I-42m (8) (8) (12) ITC-4 [In 3O(pba) 3(bpdc) 1.5](NO 3) I-43m (5) (5) (8)

19 Windows Pores Supplementary Table S2 A summary of data showing pore properties of different ITC-n. Code ITC-1 ITC-2 ITC-2NH 2 ITC-2Br ITC-3 ITC-4 Void Space (Calculated) 53.7% 68.9% 66.2% 65.1% 68.5% 72.2% d pi (Å) d pii (Å) d piii (Å) d wi (Å) d wii (Å) d wiii (Å)

20 Supplementary Table S3 Crystal data and structure refinement for ITC-1. Emperical formula C30H18In3N4O16 Formula weight Temperature 150(2) K Wavelength Å Crystal system cubic Space group I-43m (No. 217) Unit cell parameters a = b = c = (5) Å, α = β = γ = 90 o Volume (4) Å 3 Z 8 Density (calculated) g/cm 3 Absorption coefficient F(000) 3760 Crystal size 0.72 x 0.62 x 0.52 mm 3 Theta range for data collection 3.44 to Index ranges -26<=h<=3, -17<=k<=21, -26<=l<=13 Reflections collected 8354 Independent reflections 1740 [R int = ] Completeness to theta = % Absorption correction Empirical Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 1740 / 0 / 85 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.å -3

21 Supplementary Table S4 Crystal data and structure refinement for ITC-2. Emperical formula C48H30In3N4O16 Formula weight Temperature 150(2) K Wavelength Å Crystal system cubic Space group I-43m (No. 217) Unit cell parameters a = b = c = (16) Å, α = β = γ = 90 o Volume 21388(2) Å 3 Z 8 Density (calculated) g/cm 3 Absorption coefficient F(000) 4720 Crystal size 0.22 x 0.21 x 0.21 mm 3 Theta range for data collection to Index ranges -27<=h<=27, -27<=k<=24, -27<=l<=16 Reflections collected Independent reflections 3744 [R int = ] Completeness to theta = % Absorption correction Empirical Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 2083 / 294 / 160 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole 0.87 and e.å -3

22 Supplementary Table S5 Crystal data and structure refinement for ITC-2NH 2. Emperical formula C48H31.5In3N5.5O16 Formula weight Temperature 150(2) K Wavelength Å Crystal system Cubic Space group I-43m (No. 217) Unit cell parameters a = b = c = (6) Å, α = β = γ = 90 o Volume (8) Å 3 Z 8 Density (calculated) g/cm 3 Absorption coefficient F(000) 4780 Crystal size 0.30 x 0.29 x 0.28 mm 3 Theta range for data collection 1.04 to Index ranges -23<=h<=23, -29<=k<=27, -29<=l<=29 Reflections collected Independent reflections 2593 [R int = ] Completeness to theta = % Absorption correction Empirical Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 2593 / 268 / 150 Goodness-of-fit on F Final R indices [I > 2σ(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole 1.11 and e.å -3

23 Supplementary Table S6 Crystal data and structure refinement for ITC-3. Emperical formula Formula weight Temperature Wavelength Crystal system C54H33In3N4O16 150(2) K Å Tetragonal Space group I-42m (No. 121) Unit cell parameters Volume (12) Å 3 Z 8 Density (calculated) g/cm 3 F(000) 5024 Crystal size 0.57 x 0.55 x 0.52 mm 3 Theta range for data collection 0.99 to Index ranges Reflections collected a = b = (8) Å, c = (8) Å, α = β = γ = 90 o -35<=h<=27, -35<=k<=35, -30<=l<=36 Independent reflections [R int = ] Completeness to theta = % Absorption correction Empirical Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters / 548 / 402 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole 2.11 and e.å -3

24 Supplementary Table S7 Crystal data and structure refinement for ITC-4. Emperical formula C57H36In3N4O16 Formula weight Temperature 150(2) K Wavelength Å Crystal system cubic Space group I-43m (No. 217) Unit cell parameters a = b = c = (5) Å, α = β = γ = 90 o Volume (8) Å 3 Z 8 Density (calculated) g/cm 3 Absorption coefficient F(000) 5200 Crystal size 0.75 x 0.65 x 0.55 mm 3 Theta range for data collection 0.96 to Index ranges -30<=h<=29, -37<=k<=7, -37<=l<=37 Reflections collected Independent reflections 4836 [R int = ] Completeness to theta = % Absorption correction Empirical Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 4836 / 0 / 131 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.å -3

25 Supplementary Methods Synthesis of [In 3 O(ina) 3 (bdc) 1.5 ](NO 3 ) (ITC-1): In a 20 ml glass vial, 65.4 mg (0.1 mmol) of In(NO 3 ) 3 H 2 O, 23.0 mg isonicotinic acid (ina, 0.2 mmol) and 18.0 mg 1,4-benzenedicarboxylic acid (bdc, 0.1 mmol) was dissolved in 2.0 g of DMF solution. After the mixture was stirred for 20 minutes, the vial was sealed and placed in a 120 o C oven for 4 days. Pure colorless truncated cube like crystals was obtained after cooling to room temperature. The yield was about 81% based on the metal. The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2a). Synthesis of [In 3 O(pba) 3 (bdc) 1.5 ](NO 3 ) (ITC-2): In a 20 ml glass vial, 33.4 mg (0.1 mmol) of In(NO 3 ) 3 H 2 O, 20.0 mg 4-(4-pyridyl)benzoic acid (pba, 0.1 mmol) and 8.0 mg 1,4-benzene-dicarboxylic acid (bdc, 0.05 mmol) was dissolved in 2.0 g of DMA solution. After the mixture was stirred for 20 minutes, the vial was sealed and placed in a 90 o C oven for 4 days. Pure colorless truncated cube like crystals was obtained after cooling to room temperature. The yield was about 90% based on the metal. The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2b). Synthesis of [In 3 O(pba) 3 (NH 2 -bdc) 1.5 ](NO 3 ) (ITC-2NH2): The synthesis is similar to the synthesis of ICF-2 except the 1,4-benzenedicarboxylic acid (bdc) is replaced by 2-amino-1,4-benzene-dicarboxylic acid (NH 2 -bdc). The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2b). Synthesis of [In 3 O(pba) 3 (Br-bdc) 1.5 ](NO 3 ) (ITC-2Br): The synthesis is similar to the synthesis of ICF-2 except the 1,4-benzenedicarboxylic acid (bdc) is replaced by 2-bromo-1,4-benzene-dicarboxylic acid (Br-bdc). The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2b). Synthesis of [In 3 O(pba) 3 (ndc) 1.5 ](NO 3 ) (ITC-3): In a 20 ml glass vial, 32.1 mg (0.1 mmol) of In(NO 3 ) 3 H 2 O, 20.0 mg 4-(4-pyridyl)benzoic acid (pba, 0.1 mmol) and 11.0 mg 2,6-naphthalenedicarboxylic acid (ndc, 0.05 mmol) was dissolved in 2.0 g of DMA solution. After the mixture was stirred for 20 minutes, the vial was sealed and placed in a 120 o C oven for 4 days. Pure colorless truncated cube like crystals was obtained after cooling to room temperature. The yield was about 83% based on the metal. The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2c).

26 Synthesis of [In 3 O(pba) 3 (bpdc) 1.5 ](NO 3 ) (ITC-4): In a 20 ml glass vial, 31.8 mg (0.1 mmol) of In(NO 3 ) 3 H 2 O, 20.0 mg 4-(4-pyridyl)benzoic acid (pba, 0.1 mmol) and 14.0 mg biphenyldicarboxylic acid (bpdc, 0.05 mmol) was dissolved in 1.0 g of DMA solution. After the mixture was stirred for 20 minutes, the vial was sealed and placed in a 90 o C oven for 5 days. Pure colorless truncated cube like crystals was obtained after cooling to room temperature. The yield was about 86% based on the metal. The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2d). Synthesis of [Ni II 2Ni III (μ 3 -OH)(pba) 3 (bdc) 1.5 ] (solvent) (ITC-2-Ni): In a 20 ml glass vial, 30 mg Ni(NO 3 ) 2 6H 2 O was dissolved in 4.0 g of DMA and 1.0 g of methanol, then 20 mg of 4-(4-pyridyl)benzoic acid (pba, 0.1 mmol) and 8 mg of 1,4-benzenedicarboxylic acid (bdc, 0.05 mmol) was added and the mixture was stirred under room temperature for 20 minutes. Then the vial was sealed and heated at 120 o C for 4 days. Pure green cube like crystals were obtained. The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2e). Synthesis of [Ni II 2Ni III (μ 3 -OH)(pba) 3 (ndc) 1.5 ] (solvent) (ITC-3-Ni): Small modification was made compared to the previously reported procedure. In a 20 ml glass vial, 30 mg Ni(NO 3 ) 2 6H 2 O was dissolved in 4.0 g of DMA and 1.0 g of methanol, then 20 mg of 4-(4-pyridyl)benzoic acid (pba, 0.1 mmol) and 11 mg of 2,6-naphthalenedicarboxylic acid (ndc, 0.05 mmol) was added and the mixture was stirred under room temperature for 20 minutes. Then the vial was sealed and heated at 120 o C for 4 days. Pure green cube like crystals were obtained. The phase purity was identified by the powder X-ray diffraction (Supplementary Figure S2f)

27 Powder X-ray diffraction: Powder X-ray diffraction experiments were performed on a Bruker D8 Advance X-ray powder diffractometer operating at 40 kv and 40 ma (CuKα radiation, λ = Å). The data collection was performed with a step size of 0.03 and counting time of 6s per step. The 2-theta angular range is from 3 to 40. Single crystal X-ray diffraction: Single-crystal X-ray analysis was performed on a Bruker Smart APEX II CCD area diffractometer with nitrogen-flow temperature controller using graphite-monochromated MoKα radiation (λ = Å), operating in the ω and φ scan mode. The SADABS program was used for absorption correction. The structure was solved by direct methods followed by successive difference Fourier methods. All non-hydrogen atoms were refined anisotropically. Computations were performed using SHELXTL 50 and final full-matrix refinements were against F 2. Thermal analysis: The simultaneous DSC-TGA thermal analysis was performed on TA Instruments SDT Q600 in the temperature range of 30 o C to 900 o C under the flowing nitrogen atmosphere. The flow rate of the nitrogen gas was controlled at about 60 milliliters per minute. The temperature is increasing at 10 o C/min. Gas sorption measurements: N 2 gas sorption experiments were carried out on a Micromeritics ASAP 2010 surface area and pore size analyzer. Prior to the measurement, the as-synthesized sample was soaked in dichloromethane for 6 days during which period the dichloromethane bath was refreshed for twice. After filtered and dried in the vacuum oven for overnight, the sample was further dried by using the degas function of the surface area analyzer for 10 hours at 80 o C. The N 2 sorption measurements were performed at 77K.

28 Supplementary References 50 Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A 64, (2008).