Supplementary Information s11

Supplementary Information

A Homochiral Metal-Organic Nanoporous Material Capable of Enantioselective Separation and Catalysis

Jung Soo Seo, Dongmok Whang, Hyoyoung Lee, Sung Im Jun, Jinho Oh, Young Jin Jeon & Kimoon Kim*

National Creative Research Initiative Center for Smart Supramolecules and Department of Chemistry, Division of Molecular and Life Sciences Pohang University of Science and Technology San 31 Hyojadong, Pohang 790-784, Republic of Korea

Table of Contents

Experimental Synthesis of the chiral building block 1. Synthesis of L- and D-POST-1 X-ray crystallography for D-POST-1 Cation Exchange in D-POST-1 2+ Enantioselective Inclusion of Ru(2,2’-bipy)3 in D-POST-1 Preparation of N-alkylated POST-1 Anion Exchange in N-alkylated POST-1 Catalytic Activity of D-POST-1 for Transesterification Size Selectivity of D-POST-1 in Transesterification. Enantioselective Catalytic Activity of L- (and D-) POST-1.

Tables Table S1 Crystal data and structure refinement for D-POST-1 Table S2 Positional and isotropic thermal parameters for D-POST-1 Table S3 Bond lengths and angles for D-POST-1 Table S4 Anisotropic thermal parameters for D-POST-1 Table S5 Amounts of alkali metal ion and counter anions included in ion exchanged POST-1 Table S6 Enantiomeric excess value for transesterification of 2 with racemic 1-phenyl-2-propanol in the presence of L- and D-POST-1

S1 Figures Fig. S1 Crystallographic asymmetric unit for D-POST-1 3 Fig. S2 Structure of the trinuclear secondary building unit [Zn3( -O)(1- 2- H)6] in POST-1 Fig. S3 Interconnection of two neighboring trinuclear secondary building units in POST-1. Fig. S4 Schematic diagram showing how the secondary building units are linked and stacked in POST-1. Fig. S5 Powder XRD patterns for (a) air-dried POST-1, (b) after solvent removal, (c) after exposure to EtOH vapor, and (d) after exposure to water vapor. Fig. S6 Powder XRD pattern for K+ exchanged POST-1. 2+ Fig. S7 Circular dichroism (CD) spectra for Ru(2,2’-bipy)3 included in L- and D-POST-1. Fig. S8 Schematic diagram showing chemical modification of the pore environment using N-alkylation of the free pyridyl groups. Fig. S9 Degree of N-methylation of the free pyridyl groups versus reaction time. - Fig. S10 Raman spectra showing the presence of I3 counter ions in N- alkylated POST-1. Fig. S11 TGA thermograms for POST-1 and N-alkylated POST-1. Fig. S12. XRD patterns for POST-1 and N-alkylated POST-1. - - Fig. S13 IR spectra showing counter ion exchange (I3 with PF6 ) in Methyl- POST-1. - Fig. S14 IR spectra showing counter ion exchange (PF6 with p- toluenesulfonate) in Methyl-POST-1. Fig. S15 Effect of the amount of POST-1 on the rate of transesterification of 2 with ethanol. Fig. S16 Transesterification of 2 with ethanol in the absence and presence of POST-1. Fig. S17 Transesterification of 2 with various alcohols in the presence of POST-1.

S2 Experimental All chemicals were purchased commercially and used as received, without further purification except for carbon tetrachloride and pyridine. Carbon

tetrachloride and pyridine were distilled over P2O5 and KOH, respectively.

1H, 13C, and CP MAS NMR spectra were recorded on a Bruker Avance DPX300 or Avance 500 NMR spectrometer. Elemental analyses (CHN) were performed by Korea Basic Science Institute. CD spectra were obtained on a JASCO J-715 spectropolarimeter using cuvettes with path length of 1 cm. Quantitative analyses of zinc and alkali metal ions were carried out on a Spectra AA 800 atomic absorption spectrophotometer. Mass spectra were obtained on either a Kratos MS-25 (EI) or a Joel JMS-700 (FAB, high resolution) system. HPLC analyses were performed with a TSP (thermo separation products) HPLC system consisting of a Model P4000 pump, a Model UV6000LP photodiode array detector, and a Merck (R,R)-Whelk-O1 (5 m) chiral column. Thermogravimetric analyses were performed on a Perkin-

Elmer TGA6 under nitrogen atmosphere at a scan rate of 10oC/min. Fourier transformed infrared (FT-IR) spectra were recorded on a Bruker EQUINOX 55 system. X-ray powder diffraction (XRD) data were recorded on a Rigaku

D/Max 2000 diffractometer at 40 kV, 60 mA for Cu K1( =1.5406 Å) with a

o o scan speed of 2.4 /min and a step size of 0.02 in 2. Calculated powder XRD

patterns were obtained from single-crystal X-ray diffraction data using SHELXTL-XPOW program.

S3 Synthesis of the chiral building block 1.

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(4R,5R)- (and (4S,5S)-) methyl 2,2-dimethyl-5-[(4-pyridinylamino) carbonyl]-1,3- dioxolane-4-carboxylate (L- and D-5). Compounds L- and D-4 were prepared by literature method (J. Am. Chem. Soc. 1978, 100, 4865). Dicyclohexylcarbodiimide (0.71 g, 3.42 mmol) and 4-aminopyridine (0.32 g, 3.42 mmol) were added to a solution of L-4 (0.70 g, 3.42 mmol) in dry CH2Cl2 (50 mL) cooled in an ice-water bath. After the mixture was stirred for 5 h at room temperature, the byproduct dicyclohexylurea was removed by filtration. The solvent was removed in vacuo and the residue was purified by flash chromatography (SiO2, EtOAc : MeOH = 3 : 1) to give viscous oily product L- 5 (0.70 g, 73%). Using the same method, D-5 was prepared in 61% yield. 1H NMR

(CDCl3, 300 MHz)  8.70 (d, J = 6.4 Hz, 2H), 8.38 (br, 1H), 7.52 (d, J = 6.0 Hz, 2H), 4.91 (d, J = 5.0 Hz, 1H), 4.85 (d, J = 5.3 Hz, 1H), 3.88 (s, 3H), 1.57 (s, 3H), 1.54 (s,

3H); 13C NMR (CDCl3, 75 MHz)  170.7, 168.8, 151.4, 144.0, 114.4, 114.0, 78.2, 77.7, + 53.5, 27.0, 26.5; EI-MS: m/z 280.10 [M] calcd for C13H16N2O5 280.28; Anal. Calcd . for C13H16N2O5 0.6 H2O: C, 53.59; H, 5.97; N, 9.62. Found: C, 53.39; H, 5.94; N, 9.23. (4R,5R)- (and (4S,5S)-) 2,2-Dimethyl-5-[(4-pyridinyl amino)carbonyl]-1,3- dioxolane-4-carboxylic acid (L- and D-1). After a solution of KOH (0.456 g, 0.812 mmol) in anhydrous MeOH (1 mL) was added to a solution of L-5 (0.228 g, 0.812 mmol) in anhydrous MeOH (2 mL), the mixture was heated at reflux for 8 h. The mixture was cooled to room temperature and treated with 10% HNO3 in MeOH to

S4 adjust the pH of the solution to 3 - 4. After the solvent was removed in vacuo, the residue was purified by flash chromatography (SiO2, EtOAc : MeOH = 1 : 1) to give a white solid (0.155 g, 72%). Using the same method, D-1 was prepared in 80% yield. 1 H NMR (CD3OD, 300 MHz) 8.56 (d, J = 6.4 Hz, 2H), 8.00 (d, J = 6.8 Hz, 2H), 4.82

(dd, 2H), 1.50 (d, J = 8.31 Hz); 13C NMR (CD3OD, 75 MHz) 173.8, 170.8, 149.9,

146.3, 114.9, 112.9, 78.7, 77.6, 25.6, 25.4; HR FAB-MS m/z 267.0886 [M+1]+ calcd for

C12H14N2O5 267.10; Potassium salt of L-1 was used for elemental analysis. Anal.

Calcd for C12H13N2O5K0.3 MeOH: C, 47.05; H, 4.56; N, 8.92. Found: C, 47.06; H, 4.88; N, 9.19. . L- (and D-) POST-1. A solution of Zn(NO3) 2 6H2O (0.610 g, 2.54 mmol) in MeOH (10 mL) was added to a solution of L-1 (0.330 g, 1.24 mmol) in water (5 mL), pH of which had been adjusted to 8 by aqueous NaOH solution. The reaction mixture was stirred at room temperature for 2 days. Microcrystalline product L-POST-1 was filtered, washed with MeOH, and dried in the air (0.180 g, 44%). Using the same 1 method, D-POST-1 was prepared in 47% yield. H-NMR (D2O/CF3COOD)  8.22 (d, 2H), 7.83 (d, 2H), 4.46 (m, 2H), 1.12 (s, 6H); 13C CP MAS NMR:  174.5, 168.1,

149.2, 113.0, 79.2, 26.4. Anal. Calcd for [Zn3(O)(1-H)6](H3O)2(H2O)7: C, 43.95; H,

5.02; N, 8.54; Zn, 9.97. Found, C, 43.66; H, 4.93; N, 8.64; Zn, 10.27. FT-IR (KBr, 4000-370 cm-1): 3451.0 (br), 3289.3 (w), 3197.2 (w), 3097.8 (w), 2991.7 (w), 2938.5 (w), 2362.8 (w), 1713.9 (s), 1650.9 (vs), 1600.5 (vs), 1518.5 (vs), 1430.1 (s), 1384.1 (s),

1332.8 (m), 1302.8 (m), 1259.6 (m), 1213.9 (s), 1165.8 (m), 1095.5 (s), 1029.7 (m), 1002.8 (w), 976.2 (w) 874.7 (s), 835.1 (s), 761.5 (w), 668.5 (w), 591.7 (w), 591.7(m), 536.2(m). X-ray crystallography for D-POST-1. Hexagonal plate crystals of D-POST-1 suitable

for X-ray crystallography were obtained when a methanol solution of Zn(NO3) 2 (0.1 M) was allowed to diffuse slowly into an aqueous solution of D-1 (0.02 M, pH 8) at room temperature. A crystal of D-POST-1 coated with Paraton oil was

S5 transferred quickly under a cold nitrogen stream and mounted on a Siemens SMART diffractometer equipped with a graphite monochromated Mo K ( =

0.71073 Å) radiation source and a CCD detector. Intensity data were collected at – 85 oC. The data were processed with the program SAINT. The intensity data were corrected for Lorentz and polarization effects. Semi-empirical absorption correction based on multiple reflections was also applied. The structure was solved by a combination of Patterson methods and successive difference Fourier techniques using Siemens SHELXTL-PC software package. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included at the calculated positions except for those of guest water molecules. The final cycles of the full-matrix least-squares refinements in F2 were converged to the R factors given in Table S1, which also summarizes crystallographic information for D- POST-1. Atomic coordinates, bond distances and angles, and anisotropic displacement parameters are given in Tables S2, S3, and S4, respectively. The structure of L-POST-1 is identical to that of D-POST-1 except for the opposite handedness, which has been confirmed by single crystal X-ray crystallography. Cation Exchange in POST-1. After POST-1 (150 mg) was added to alkali metal salts of p-toluenesulfonate in MeOH (40 mL, 0.05 M), the mixture was vigorously stirred by Vortex for 1 min and then allowed to stand overnight. The solid was filtered, washed with ethanol and acetone, and dried in the air. The amounts of alkali metal

ions and zinc ions were determined by atomic absorption spectroscopy. The amounts of p-toluenesulfonate included in the samples were determined by 1H

NMR spectroscopy after dissolving the samples in D2O containing a drop of

deuterated trifluoroacetic acid. The results are summarized in Table S5. 2+ Enantioselective Inclusion of Ru(2,2’-bipy)3 in D-POST-1. Microcrystalline

powder of D-POST-1 (20 mg) was suspended in an aqueous solution of Ru(2,2’-

bipy)3Cl2 (10 mL, 0.05 M). The mixture was stirred for 4 days at room

S6 temperature. The solid was filtered, washed with ethanol and acetone, and dried in the air. The amounts of the Ru complex included in the samples were determined 1 by H NMR spectroscopy after dissolving the samples in D2O containing a drop of

deuterated trifluoroacetic acid. To determine the enantioselectivity of the inclusion process, a sample of D-POST-1 including the Ru complex was dissolved in dilute nitric acid. The concentration and the enantiomeric excess (ee) value of the Ru complex included were determined by UV-Vis and circular dichroism (CD) spectroscopy, respectively, using a standard solution of enantiomerically pure - -5 bis(tris(2,2’-bipyridine)-ruthenium(II) L-tartarate as a reference (8.23 x 10 M). In a similar fashion, enantioselective inclusion of the Ru complex in L-POST-1 was also studied. The results are shown in Figure S7. Preparation of N-Methylated POST-1 (Methyl-POST-1). To a solution of methyl iodide (3.968 g, 27.96 mmol) in DMF (2.5 mL) was added POST-1 (156 mg; containing 0.51 mmol of exposed pyridyl groups) and the mixture was stirred for 2 h. The pale yellow solid was filtered, washed with ethanol and acetone, and dried in the air (121 mg, 76%). Degree of N-methylation versus reaction time is shown in Figure S9. – – Elemental analysis data is consistent with the fact that I3 , instead of I , is included as counterion in the product, which has been confirmed by Raman spectroscopy (Figure

S10). 1H NMR (a drop of CF3COOD in D2O)  8.27 (m, 4H), 7.88 (m, 4H), 4.70 (m, 4H), 3.91 (s, 3H), 1.20 (s, 12H). 13C CP MAS NMR  174.4, 169.4, 150.3, 146.0,

113.4, 80.1, 48.2, 27.1. Anal. Calcd for [Zn3(O)(1-H)3(1-Me)3(I3)](DMF)(H2O)6: C, 38.86; H, 4.43; N, 7.55; Zn, 8.14. Found, C, 38.70; H, 4.79; N, 7.41; Zn, 7.94. FT-IR (KBr, 4000-370 cm-1): 3449.1 (br), 3341.1 (w), 3245.6 (w), 3150.2 (w), 3050.8 (w), 2948.6 (w), 2896.6 (w), 2316.1 (w), 1674.9 (m), 1610.3 (s), 1558.2 (vs), 1475.3 (s), 1389.5 (m), 1343.2 (m), 1291.2 (w), 1260.3 (w), 1218.8 (w), 1172.5 (s), 1123.3 (sh), 1055.8 (s), 988.3 (sh), 934.3 (w), 881.3 (w), 834.1 (m), 792.6 (m), 719.3 (w), 625.8 (w), 549.6 (w), 494.7(m).

S7 Preparation of N-Hexylated D-POST-1 (Hexyl-D-POST-1). To a solution of 1- iodohexane (4.038 g, 28.45 mmol) in DMF (1.5 mL) was added D-POST-1 (154 mg, containing 0.50 mmol of exposed pyridyl groups) and the mixture was stirred for 1 h at room temperature, and then at 50 oC for 4 h. The pale yellow solid was filtered, washed with ethanol and acetone, and dried in the air (95.6 mg, 55%). 1H NMR (a drop of

CF3COOD in D2O, 300 MHz)  7.83 (m, 2H ,PyHb), 7.81 (m, 2H, PyHa), 4.22 (m, 4H,

-CH-), 3.62 (m, 2H, -CH2-), 1.12 (m, 2H, -CH2-), 0.72 (m, 12H, -C(CH3)-), 0.47 (m, 13 6H, -CH2CH2CH2-), 0.00 (t, 3H, -CH3); C CP MAS NMR  171.8 (s, -COO-), 167.4 + (s, -CONH-), 165.1 (s, -CONH-), 147.6 (s, -CONHC=), 142.0 (s, -PyCb ), 77.0 (s,

(CH3)2C(O)2(COO)(CONH-)), 58.1 (s, Py+-(CH2)5CH3), 29.0 (Py+-

(CH2)3CH2CH2CH3), 28.2 (s, Py+-CH2CH2(CH2)3CH3), 19.8 (s, Py+-

(CH2)4CH2CH3), 11.7 (s, Py+-(CH2)5CH3). Anal. Calcd for [Zn3(O)(1-H)3(1-

Hex)3(I3)](DMF)(H2O)5.5: C, 42.76; H, 5.21; N, 6.97; Zn, 7.51 Found, C, 43.06; H,

5.25; N, 6.89; Zn, 7.50. FT-IR (KBr, 4000-370 cm-1) 3449.1 (br), 3286.6 (w), 3195.6 (w), 3113.4 (w), 3047.5 (w), 2989.8 (w), 2933.1 (w), 2862.3 (w), 2365.1 (w), 1718.9 (m), 1646.0 (vs), 1602.4 (vs), 1520.5 (vs), 1464.2 (m), 1429.6 (m), 1382.4 (m), 1328.0 (m), 1257.9 (sh), 1213.6 (m), 1183.0 (m), 1167.41 (m), 1091.5 (m), 1027.3 (sh), 976.3 (w), 868.0 (m), 837.4 (m), 765.0 (w), 697.1 (w), 589.2 (w), 536.2 (w).

S8 - Anion Exchange in N-alkylated POST-1. The exchange of I3 ion in Methyl-POST-1 - with PF6 ion was conducted by mixing sodium hexafluorophosphate (85 mg,

0.50 mmol) and Methyl-POST-1 (63 mg, 0.031 mmol) in DMF (3 mL), and then stirring the mixture for 6 h. The mixture was filtered, washed with ethanol and acetone, and dried in the air. The anion exchange was confirmed by IR - spectroscopy (Figure S13). The PF6 in Methyl-POST-1 was in turn exchanged - with p-toluenesulfonate. A sample of Methyl-POST-1 containing PF6 (37 mg)

was suspended in a solution of sodium p-toluenesulfonate (47 mg, 0.24 mmol) in DMF (3 mL) and the mixture was stirred for 2 h. The anion exchange reaction was monitored by IR spectroscopy (Figure S14). Catalytic Activity of D-POST-1 for transesterfication reaction.

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2,4-Dinitrophenyl acetate (100 mg, 0.44 mmol) and EtOH (4 eqiv) were added to a suspension of D-POST-1 (27 mg, 10%) in CCl4 (1.0 mL) and the mixture was stirred at 27°C in a shaking incubator. The reaction was monitored by taking an aliquot (0.05 mL) of the reaction mixture in a given interval and determining the amounts of ethyl acetate and 2,4-dinitrophenol by 1H NMR spectroscopy. Before used as catalysts, freshly prepared POST-1 and Methyl-POST-1 were soaked in ethanol for a few hours to exchange water molecules with ethanol molecules inside the channels and dried in the air. They had crystallinity and maintained it during the catalytic reaction as judged by visual examination under an optical microscope and/or by powder X-ray diffraction patterns before and after the reaction. The same experiment was repeated without catalyst, and with D-POST-1 (13 mg, 5%), D-POST-1 (40 mg, 15%), D-POST-1 (53 mg, 20%), Methyl-D-POST-1 (100% N-methylated, 33 mg, 10%), Methyl-D-POST-1

S9 (35% N-methylated, 29 mg, 10%), and 5 (12 mg, 10%) as catalysts. When 5 was used as the catalyst the reaction mixture was homogeneous. The results are illustrated in Figures S15 and S16. Size Selectivity of D-POST-1 in transesterification.

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A mixture of 2,4-dinitrophenyl acetate (50 mg, 0.22 mmol), ROH (R = ethyl (41.0 mg, 0.88 mmol), 2-methyl-1-propyl (67.0 mg, 0.88 mmol), neopentyl (78.0 mg, 0.88 mmol), and 3,3,3-triphenyl-1-propyl (253 mg, 0.88 mmol)), and catalyst (5 (6.2 mg, 10%), D- POST-1 (13 mg, 10%), or Methyl-D-POST-1 (35% N-methylated, 14 mg, 10%)) in CCl4 (1 mL) was stirred at 27°C in a shaking incubator. The reaction mixture was heterogeneous except for the case when 5 was used as the catalyst. The reaction was monitored by 1H NMR spectroscopy. The results are shown in Figure S17. Enantioselective Catalytic Activity of L- (and D-) POST-1. A mixture of 2,4-dinitrophenyl acetate (100 mg, 0.44 mmol), 1-phenyl-2-propanol (241 mg, 1.76 mmol), and (L or D)-POST-1 (27 mg, 10%) in CCl4 (2 mL) was stirred at

27°C in a shaking incubator. After 57 h, the product 1-phenyl-2-propyl acetate (18% conversion as determined by 1H NMR spectroscopy) was isolated and purified by column chromatography. The enantiomeric excess value of the product was determined by HPLC (chiral column: (R,R)-Whelk-O1 (5 m), Merck, flow rate: 0.3 mL/min, isopropanol : hexane = 0.5 : 99.5, UV detector, wavelength: 254 nm). In a control experiment, pyridine was used as the catalyst. The results are summarized in Table S6.

S10 Table S1. Crystal data and structure refinement for D-POST-1.

Empirical formula C72H98N12O40Zn3 Formula weight 1967.75 Temperature 188(2) K Wavelength 0.71073 Å Crystal system Trigonal Space group P321 Unit cell dimensions a = 20.9415(6) Å = 90°. b = 20.9415(6) Å = 90°. c = 15.4720(6) Å  = 120°. Volume 5876.1(3) Å3 Z 2 Density (calculated) 1.112 Mg/m3 Absorption coefficient 0.681 mm-1 F(000) 2048 Crystal size 0.15 x 0.5 x 0.5 mm3  range for data collection 1.73 to 24.16°. Index ranges -23<=h<=23, -16<=k<=23, -17<=l<=17 Reflections collected 23489 Independent reflections 6109 [R(int) = 0.0748] Completeness to  = 24.16° 98.8 % Absorption correction Semi empirical (SADABS) Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 6109 / 0 / 387 Goodness-of-fit on F2 1.092 Final R indices [I>2(I)] R1 = 0.1017, wR2 = 0.2720 R indices (all data) R1 = 0.1258, wR2 = 0.2967 Absolute structure parameter 0.05(4) Largest diff. peak and hole 0.791 and -0.475 e.Å-3

S11 Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2 x 103) for D-POST-1. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) Zn 4179(1) 6460(1) 8903(1) 76(1) O(1) 3333 6667 8800(14) 111(6) O(2) 4639(4) 7080(4) 7746(7) 100(3) O(3) 4480(4) 8033(4) 8060(6) 93(3) O(4) 5152(8) 7545(9) 6230(9) 145(5) O(5) 4722(7) 8162(6) 5347(8) 126(4) O(6) 5117(6) 9500(6) 6192(9) 136(4) O(7) 3720(4) 5849(5) 10056(7) 103(3) O(8) 2517(4) 5145(3) 9695(6) 83(2) O(9) 3533(4) 5211(4) 11544(6) 85(2) O(10) 2555(4) 4967(5) 12392(7) 96(3) O(11) 1314(4) 3850(4) 11388(7) 92(3) O(1W) -2470(20) 1340(20) 11190(20) 240(20) O(2W) 0 6549(19) 10000 510(60) O(3W) 6234(18) 10000 5000 290(20) O(4W) 2595(13) 11328(12) 6850(20) 280(20) N(1) 3911(7) 8888(5) 6591(9) 107(4) N(2) 3307(11) 10515(8) 6716(17) 164(8) N(3) 1143(4) 4844(4) 11203(7) 77(3) N(4) -1149(4) 3910(4) 11061(7) 74(3) C(1) 4686(6) 7686(6) 7580(10) 81(3) C(2) 5018(9) 7998(10) 6788(12) 115(5) C(4) 5166(11) 7762(11) 5340(16) 135(6) C(3) 4499(7) 8173(7) 6198(10) 96(4) C(5) 5893(18) 8310(20) 5010(20) 290(20) C(6) 4727(14) 7058(13) 4759(17) 190(11) C(7) 4561(12) 8954(9) 6311(11) 120(6) C(8) 3752(8) 9444(7) 6614(11) 101(4) C(9) 4291(12) 10199(8) 6441(15) 147(8) C(10) 3945(18) 10704(11) 6567(19) 171(10) C(11) 2793(15) 9822(15) 6841(19) 180(11) C(12) 3013(11) 9247(9) 6829(14) 132(7)

S12 C(13) 3055(6) 5334(6) 10163(8) 70(3) C(14) 2915(6) 4947(6) 10951(10) 87(4) C(16) 3272(6) 5020(7) 12404(10) 88(4) C(15) 2373(5) 5067(6) 11529(8) 75(3) C(17) 3776(8) 5622(9) 12986(12) 133(6) C(18) 3210(13) 4291(12) 12641(14) 152(7) C(19) 1548(6) 4515(6) 11374(9) 84(3) C(20) 379(5) 4496(5) 11141(8) 75(3) C(21) -79(6) 3748(7) 11126(8) 81(3) C(22) -856(5) 3467(6) 11068(9) 83(4) C(23) -663(6) 4636(6) 11104(9) 90(4) C(24) 87(6) 4949(7) 11100(10) 96(4)

S13 Table S3. Bond lengths [Å] and angles [°] for D-POST-1.

Zn-O(1) 2.029(2) Zn-N(4)#1 2.095(7) Zn-O(8)#2 2.109(7) Zn-O(7) 2.126(11) Zn-O(2) 2.136(11) Zn-O(3)#3 2.171(7) O(1)-Zn#2 2.029(2) O(1)-Zn#3 2.029(2) O(2)-C(1) 1.250(14) O(3)-C(1) 1.257(12) O(3)-Zn#2 2.171(7) O(4)-C(2) 1.410(18) O(4)-C(4) 1.45(2) O(5)-C(3) 1.401(17) O(5)-C(4) 1.53(2) O(6)-C(7) 1.169(19) O(7)-C(13) 1.276(13) O(8)-C(13) 1.226(12) O(8)-Zn#3 2.109(7) O(9)-C(16) 1.418(16) O(9)-C(14) 1.452(14) O(10)-C(15) 1.432(15) O(10)-C(16) 1.449(13) O(11)-C(19) 1.225(13) N(1)-C(7) 1.37(2) N(1)-C(8) 1.361(17) N(2)-C(10) 1.21(3) N(2)-C(11) 1.32(3) N(3)-C(19) 1.358(14) N(3)-C(20) 1.390(12) N(4)-C(23) 1.344(13) N(4)-C(22) 1.343(13) N(4)-Zn#4 2.095(7) C(1)-C(2) 1.40(2) C(2)-C(3) 1.60(2) C(4)-C(5) 1.46(3) C(4)-C(6) 1.57(3) C(3)-C(7) 1.58(2) C(8)-C(12) 1.43(2) C(8)-C(9) 1.44(2) C(9)-C(10) 1.56(3) C(11)-C(12) 1.49(3) C(13)-C(14) 1.412(17) C(14)-C(15) 1.561(16) C(16)-C(17) 1.477(19) C(16)-C(18) 1.51(2) C(15)-C(19) 1.544(15) C(20)-C(24) 1.366(17) C(20)-C(21) 1.367(16) C(21)-C(22) 1.430(14) C(23)-C(24) 1.365(15) O(1)-Zn-N(4)#1 171.5(3) O(1)-Zn-O(8)#2 96.6(4) N(4)#1-Zn-O(8)#2 91.6(3) O(1)-Zn-O(7) 90.8(6) N(4)#1-Zn-O(7) 87.3(3) O(8)#2-Zn-O(7) 87.4(3) O(1)-Zn-O(2) 89.0(6) N(4)#1-Zn-O(2) 92.9(4) O(8)#2-Zn-O(2) 92.4(3) O(7)-Zn-O(2) 179.7(3) O(1)-Zn-O(3)#3 87.2(4) N(4)#1-Zn-O(3)#3 84.7(3) O(8)#2-Zn-O(3)#3 175.9(3) O(7)-Zn-O(3)#3 94.1(3) O(2)-Zn-O(3)#3 86.1(3) Zn#2-O(1)-Zn#3 119.40(17)

S14 Zn#2-O(1)-Zn 119.40(17) Zn#3-O(1)-Zn 119.40(17) C(1)-O(2)-Zn 124.9(8) C(1)-O(3)-Zn#2 134.5(7) C(2)-O(4)-C(4) 110.6(15) C(3)-O(5)-C(4) 108.4(14) C(13)-O(7)-Zn 126.2(8) C(13)-O(8)-Zn#3 127.8(6) C(16)-O(9)-C(14) 109.9(8) C(15)-O(10)-C(16) 110.0(10) C(7)-N(1)-C(8) 125.4(13) C(10)-N(2)-C(11) 123.2(19) C(19)-N(3)-C(20) 126.3(9) C(23)-N(4)-C(22) 115.6(7) C(23)-N(4)-Zn#4 119.6(6) C(22)-N(4)-Zn#4 124.6(6) O(2)-C(1)-O(3) 126.2(13) O(2)-C(1)-C(2) 115.1(11) O(3)-C(1)-C(2) 118.7(12) C(1)-C(2)-O(4) 116.1(15) C(1)-C(2)-C(3) 111.8(12) O(4)-C(2)-C(3) 101.1(12) C(5)-C(4)-O(4) 115(2) C(5)-C(4)-O(5) 104.8(16) O(4)-C(4)-O(5) 103.9(16) C(5)-C(4)-C(6) 115(2) O(4)-C(4)-C(6) 109.9(17) O(5)-C(4)-C(6) 106.7(15) O(5)-C(3)-C(7) 105.4(11) O(5)-C(3)-C(2) 105.2(12) C(7)-C(3)-C(2) 117.4(14) O(6)-C(7)-N(1) 127.0(17) O(6)-C(7)-C(3) 121.4(19) N(1)-C(7)-C(3) 111.6(13) N(1)-C(8)-C(12) 116.9(12) N(1)-C(8)-C(9) 123.0(15) C(12)-C(8)-C(9) 120.1(14) C(8)-C(9)-C(10) 110.4(19) N(2)-C(10)-C(9) 127.7(19) N(2)-C(11)-C(12) 118(2) C(8)-C(12)-C(11) 120.0(18) O(8)-C(13)-O(7) 129.4(12) O(8)-C(13)-C(14) 115.6(10) O(7)-C(13)-C(14) 115.0(10) C(13)-C(14)-O(9) 115.9(9) C(13)-C(14)-C(15) 111.2(9) O(9)-C(14)-C(15) 99.1(10) O(9)-C(16)-C(17) 108.7(11) O(9)-C(16)-O(10) 104.3(9) C(17)-C(16)-O(10) 110.1(12) O(9)-C(16)-C(18) 109.8(13) C(17)-C(16)-C(18) 112.3(14) O(10)-C(16)-C(18) 111.2(13) O(10)-C(15)-C(19) 108.4(9) O(10)-C(15)-C(14) 104.0(9) C(19)-C(15)-C(14) 115.0(10) O(11)-C(19)-N(3) 125.8(10) O(11)-C(19)-C(15) 120.6(10) N(3)-C(19)-C(15) 113.5(9) C(24)-C(20)-C(21) 119.5(8) C(24)-C(20)-N(3) 115.9(9) C(21)-C(20)-N(3) 124.6(10) C(20)-C(21)-C(22) 118.4(9) N(4)-C(22)-C(21) 122.3(9) N(4)-C(23)-C(24) 125.5(10) C(20)-C(24)-C(23) 118.3(11) Symmetry transformations used to generate equivalent atoms: #1 x-y+1, -y+1, -z+2 #2 -y+1, x-y+1, z #3 -x+y, -x+1, z #4 x-y, -y+1, -z+2

S15 Table S4. Anisotropic displacement parameters (Å2 x 103) for D-POST-1. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

U11 U22 U33 U23 U13 U12 Zn 34(1) 46(1) 157(1) -28(1) -17(1) 27(1) O(1) 34(4) 34(4) 270(20) 0 0 17(2) O(2) 64(5) 64(5) 185(9) -41(5) -18(5) 43(4) O(3) 63(4) 44(4) 170(8) 4(4) 38(5) 24(3) O(4) 146(11) 183(14) 165(10) 4(10) 34(9) 127(11) O(5) 132(9) 89(7) 163(10) -5(6) 4(8) 59(7) O(6) 100(8) 67(6) 204(12) 19(7) 31(8) 12(6) O(7) 50(5) 90(6) 190(9) -62(6) -48(5) 51(5) O(8) 45(4) 32(3) 167(7) 4(4) -35(4) 15(3) O(9) 41(4) 78(5) 133(7) 17(5) -1(4) 28(4) O(10) 45(4) 84(6) 151(8) 15(5) 6(5) 27(4) O(11) 39(4) 37(4) 201(8) 8(4) 2(5) 19(3) O(1W) 350(50) 250(40) 260(40) -20(30) -50(30) 260(40) O(2W) 170(40) 130(30) 1230(150) 60(30) 120(60) 80(20) O(3W) 300(40) 190(30) 350(40) 110(30) 54(13) 93(14) O(4W) 190(20) 137(19) 560(50) -80(20) -120(30) 123(18) N(1) 84(8) 50(5) 185(11) 25(6) 29(8) 32(5) N(2) 122(13) 55(8) 310(30) -17(11) -10(16) 40(9) N(3) 30(4) 35(4) 157(8) 7(5) -4(4) 10(3) N(4) 25(3) 46(5) 151(8) -37(5) -14(4) 16(3) C(1) 48(6) 59(7) 141(11) -17(7) 17(6) 30(5) C(2) 78(9) 106(11) 169(15) -40(11) -5(10) 54(9) C(4) 113(13) 101(13) 200(18) 30(13) 15(13) 61(11) C(3) 86(8) 52(7) 142(12) 14(7) 33(8) 29(6) C(5) 240(30) 440(60) 330(40) 230(40) 170(30) 280(40) C(6) 190(20) 143(18) 270(30) -70(19) 10(20) 107(18) C(7) 120(14) 73(9) 141(13) 5(9) 23(11) 29(10) C(8) 76(8) 57(7) 173(14) 7(8) -6(9) 35(6) C(9) 139(15) 47(7) 250(20) 22(10) -28(14) 42(9) C(10) 170(20) 66(11) 250(30) 7(14) -10(20) 45(14) C(11) 160(20) 160(20) 250(30) -90(20) -70(20) 110(20)

S16 C(12) 129(15) 70(9) 200(20) -6(10) -12(13) 53(10) C(13) 57(7) 56(6) 114(9) -8(6) -11(6) 42(5) C(14) 45(6) 56(6) 166(12) 3(7) 3(6) 31(5) C(16) 38(5) 84(8) 136(11) 6(8) -11(6) 26(6) C(15) 39(5) 56(6) 130(10) 2(6) 1(5) 24(4) C(17) 53(8) 111(12) 198(16) -30(11) -21(9) 14(8) C(18) 166(19) 133(16) 178(17) 34(13) 1(14) 90(15) C(19) 48(6) 57(7) 149(10) -4(6) -7(6) 29(5) C(20) 38(5) 42(5) 132(9) -24(6) -15(5) 9(4) C(21) 40(5) 85(8) 141(10) 5(7) 6(6) 47(6) C(22) 30(5) 46(6) 167(12) -17(6) -4(6) 16(4) C(23) 43(5) 46(6) 181(12) -40(7) -17(6) 21(5) C(24) 34(5) 56(6) 186(13) -35(7) -9(6) 13(5)

S17 Table S5. Amounts of alkali metal ion and counteranions (p-toluenesulfonate) included in alkali metal ion exchanged POST-1.

alkali metal No. of cations (A)a No. of anions (B)a A–Ba,b

Na+ 1.78 0.22 1.56 K+ 1.71 0.35 1.36 Rb+ 0.96 0.15 0.81 a 2- No. of ions per secondary building unit [Zn3(O)(1-H)6] . bNet cation exchange in POST-1 is given by A–B.

Table S6. Enantiomeric excess (ee) value for the transesterification of 2 with racemic alcohol 3 in the presence of L- and D-POST-1

catalyst S (%) R (%) ee (%)

L-POST-1 (R,R) 45.9 54.1 8.2 D-POST-1 (S,S) 54.2 45.9 8.3 Pyridine 49.6 50.5 0.9

S18 Figure Captions

Figure S1. Crystallographic asymmetric unit for D-POST-1.

3 2- Figure S2. Structure of the trinuclear secondary building unit [Zn3( -O)(1-H)6] in POST-1 showing coordination geometry of the zinc ions. Only the zinc ions, bridging oxo, carboxylate groups and pyridyl groups are shown for clarity. Figure S3. Interconnection of two neighboring trinuclear secondary building units in POST-1. Each trinuclear unit donates one pyridyl group to a neighboring trinuclear unit, and at the same time accepts a pyridyl group from the neighbor. The noncoordinating pyridyl groups are highlighted by gray shade. Figure S4. (a) Schematic diagram showing how the secondary building units (represented by circles) are linked together to form a 2-D layer in POST-1. The trinuclear center is offset by 6.2 Å along the c axis with respect to three directly connected neighboring units in the 2-D layer. (b) The 2-D layers stack along the c axis with a mean interlayer separation of 15.47 Å (the secondary building units are represented by rectangles). The structure is apparently stabilized by efficient van der Waals interactions between the 2-D layers arising from their self-complementary structure. Figure S5. Powder X-ray diffraction (XRD) patterns for (a) air-dried POST-1, (b) POST-1 after removal of solvate water molecules by evacuation, (c) after exposure of the evacuated POST-1 to EtOH vapor, (d) after exposure of the evacuated POST-1 to water vapor. Comparison of the observed and calculated powder XRD patterns confirms that the structure of microcrystalline POST-1 is the same as that of single crystal POST-1. Figure S6. XRD pattern for K+ ion exchanged POST-1 indicating that the framework structure of POST-1 remains unchanged upon the cation exchange. Figure S7. Circular dichroism (CD) spectra for (a) optically pure [

2+ -Ru(2,2’-bipy)3] L-tartarate, (b) Ru(2,2’-bipy)3 included L-POST-1, (c) Ru(2,2’-bipy)

2+ 2+ 3 adsorbed on a simple 3:1 mixture of Ligand D-1 and zinc nitrate, (d) Ru(2,2’-bipy) 3 included D-POST-1.

S19 Figure S8. Schematic diagram showing chemical modification of the pore environment using N-alkylation of the free pyridyl groups exposed in the channels. Figure S9. Degree of N-methylation of the free pyridyl groups versus reaction time. Reaction conditions: see the experimental section. Figure S10. Raman spectra showing the presence of I3- counterions in the N-alkylated POST-1 (a) POST-1, (b) Methyl-POST-1, (c) Hexyl-POST-1. Figure S11. TGA thermograms for POST-1 and N-alkylated POST-1 which channels had been filled with DMF molecules. The thermograms show that 25, 21, and 10% of DMF are included in POST-1, Methyl-POST-1, and Hexyl-POST-1, respectively, which means that the pore volume of POST-1 shrinks by 14% and 60% upon alkylation with iodomethane (CH3I) and 1-iodohexane (CH3(CH2)5I), respectively. Figure S12. XRD patterns for (a) POST-1, (b) Methyl-POST-1, and (c) Hexyl-POST- 1. These results indicate that the overall framework structure of POST-1 remains unchanged upon N-alkylation of the pyridyl groups exposed in the channels. Figure S13. IR spectra of Methyl-POST-1 showing exchange of counterion I3- with

- PF6 .

- Figure S14. IR spectra of Methyl-POST-1 showing exchange of counterion PF6 with

- p-toluenesulfonate. All the PF6 peaks disappear with the concomitant appearance of p- toluenesulfonate peaks in 30 min. Figure S15. Effect of the amount of the catalyst POST-1 on the rate of transesterification of 2 (100 mg, 0.44 mmol) with ethanol (2 : EtOH = 1 : 4) in CCl4 (2 ml) at 27°C: (a) 20 mol %, (b) 15 mol %, (c) 10 mol %, (d) 5 mol %, (e) no catalyst. Figure S16. Transesterification of 2 (50 mg, 0.22 mmol) with ethanol (2 : alcohol = 1 :

4) in CCl4 (1 ml) at 27°C in the presence of POST-1 (10 mol%) (a), 35%-N-methyl- POST-1 (10 mol%) (b), and 100%-N-methyl-POST-1 (10 mol%) (c) as catalysts. Notice that the catalytic activity of POST-1 is significantly reduced by partial N- methylation of the pyridyl groups exposed in the channels. The catalytic activity observed for 100%-N-methylated POST-1 is presumably due to free pyridyl groups newly exposed upon slow decomposition of the catalyst during the stirring process. N- methylated POST-1 has somewhat lower stability than POST-1 itself as also seen in the TGA thermogram (Figure S11). In sum, these results support the idea that the free

S20 pyridyl groups exposed in the channels (and also those exposed to the surface) in POST-1 behave as catalytic centers. Figure S17. Transesterification of 2 with ethanol (solid square), 2-methyl-1-propanol (solid circle), neopentanol (solid triangle), and 3,3,3-triphenyl-1-propanol (+) (2 : alcohol = 1 : 4) in CCl4 at room temperature in the presence of POST-1 (10 mol%, suspension) (solid lines) and 5 (10 mol%, homogeneous solution) (dashed lines) as catalysts. When 5 is used as the catalyst, transesterification of 2 with all the primary alcohols occurs with comparable reaction rates. In the presence of POST-1 as the catalyst, however, transesterification of 2 with alcohols bulkier than ethanol occurs much slowly or negligibly. Such size selectivity supports that the catalysis mainly occurs in the channels.