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
Enantioselective Inclusion of Ru(2,2’-bipy)32+ 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
Fig. S2 Structure of the trinuclear secondary building unit [Zn3(3-O)(1H)6]2- 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.
Fig. S7 Circular dichroism (CD) spectra for Ru(2,2’-bipy)32+ included in Land 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 Nalkylated 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 ptoluenesulfonate) 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. Xray 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
scan speed of 2.4o/min and a step size of 0.02o 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.
--------------------------------------------------------------------------------------------------------
--------------------------------------------------------------------------------------------------------
(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]-1,3dioxolane-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% HNO 3
S4
in MeOH to 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.
1H
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 method, D-POST-1 was prepared in 47% yield.
1H-
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
S5
of D-1 (0.02 M, pH 8) at room temperature. A crystal of D-POST-1 coated
with Paraton oil was 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
o
C.
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 nonhydrogen 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
S6
dissolving the samples in D2O containing a drop of deuterated
trifluoroacetic acid. The results are summarized in Table S5.
Enantioselective Inclusion of Ru(2,2’-bipy)32+ 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 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 by 1H 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 DPOST-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 -bis(tris(2,2’-bipyridine)-ruthenium(II) L-tartarate as a reference (8.23
x 10-5 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.
S7
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).
Preparation of N-Hexylated D-POST-1 (Hexyl-D-POST-1). To a solution of 1iodohexane (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, 6H, -CH2CH2CH2-), 0.00 (t, 3H, CH3); 13C 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).
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
S8
(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.
--------------------------------------------------------------------------------------------------------
--------------------------------------------------------------------------------------------------
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-DPOST-1 (35% N-methylated, 29 mg, 10%), and 5 (12 mg, 10%) as catalysts.
S9
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.
--------------------------------------------------------------------------------------------------------
--------------------------------------------------------------------------------------------------------
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-2propanol (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 1phenyl-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
Temperature
Wavelength
Crystal system
Space group
1967.75
188(2) K
0.71073 Å
Trigonal
P321
Unit cell dimensions
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
Crystal size
 range for data collection
a = 20.9415(6) Å
b = 20.9415(6) Å
c = 15.4720(6) Å
5876.1(3) Å3
2
1.112 Mg/m3
0.681 mm-1
2048
0.15 x 0.5 x 0.5 mm3
1.73 to 24.16°.
Index ranges
Reflections collected
Independent reflections
Completeness to  = 24.16°
Absorption correction
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2(I)]
-23<=h<=23, -16<=k<=23, -17<=l<=17
23489
6109 [R(int) = 0.0748]
98.8 %
Semi empirical (SADABS)
Full-matrix least-squares on F2
6109 / 0 / 387
1.092
R1 = 0.1017, wR2 = 0.2720
R indices (all data)
Absolute structure parameter
Largest diff. peak and hole
R1 = 0.1258, wR2 = 0.2967
0.05(4)
0.791 and -0.475 e.Å-3
S11
= 90°.
= 90°.
 = 120°.
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
Zn
O(1)
O(2)
O(3)
y
z
U(eq)
4179(1)
3333
4639(4)
4480(4)
6460(1)
6667
7080(4)
8033(4)
8903(1)
8800(14)
7746(7)
8060(6)
76(1)
111(6)
100(3)
93(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
O(1W)
O(2W)
5152(8)
4722(7)
5117(6)
3720(4)
2517(4)
3533(4)
2555(4)
1314(4)
-2470(20)
0
7545(9)
8162(6)
9500(6)
5849(5)
5145(3)
5211(4)
4967(5)
3850(4)
1340(20)
6549(19)
6230(9)
5347(8)
6192(9)
10056(7)
9695(6)
11544(6)
12392(7)
11388(7)
11190(20)
10000
145(5)
126(4)
136(4)
103(3)
83(2)
85(2)
96(3)
92(3)
240(20)
510(60)
O(3W)
O(4W)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(4)
6234(18)
2595(13)
3911(7)
3307(11)
1143(4)
-1149(4)
4686(6)
5018(9)
5166(11)
10000
11328(12)
8888(5)
10515(8)
4844(4)
3910(4)
7686(6)
7998(10)
7762(11)
5000
6850(20)
6591(9)
6716(17)
11203(7)
11061(7)
7580(10)
6788(12)
5340(16)
290(20)
280(20)
107(4)
164(8)
77(3)
74(3)
81(3)
115(5)
135(6)
C(3)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
4499(7)
5893(18)
4727(14)
4561(12)
3752(8)
4291(12)
3945(18)
2793(15)
3013(11)
8173(7)
8310(20)
7058(13)
8954(9)
9444(7)
10199(8)
10704(11)
9822(15)
9247(9)
6198(10)
5010(20)
4759(17)
6311(11)
6614(11)
6441(15)
6567(19)
6841(19)
6829(14)
96(4)
290(20)
190(11)
120(6)
101(4)
147(8)
171(10)
180(11)
132(7)
S12
C(13)
C(14)
C(16)
C(15)
C(17)
C(18)
C(19)
C(20)
3055(6)
2915(6)
3272(6)
2373(5)
3776(8)
3210(13)
1548(6)
379(5)
5334(6)
4947(6)
5020(7)
5067(6)
5622(9)
4291(12)
4515(6)
4496(5)
10163(8)
10951(10)
12404(10)
11529(8)
12986(12)
12641(14)
11374(9)
11141(8)
70(3)
87(4)
88(4)
75(3)
133(6)
152(7)
84(3)
75(3)
C(21)
C(22)
C(23)
C(24)
-79(6)
-856(5)
-663(6)
87(6)
3748(7)
3467(6)
4636(6)
4949(7)
11126(8)
11068(9)
11104(9)
11100(10)
81(3)
83(4)
90(4)
96(4)
S13
Table S3. Bond lengths [Å] and angles [°] for D-POST-1.
Zn-O(1)
Zn-O(8)#2
Zn-O(2)
O(1)-Zn#2
O(2)-C(1)
O(3)-Zn#2
2.029(2)
2.109(7)
2.136(11)
2.029(2)
1.250(14)
2.171(7)
Zn-N(4)#1
Zn-O(7)
Zn-O(3)#3
O(1)-Zn#3
O(3)-C(1)
O(4)-C(2)
2.095(7)
2.126(11)
2.171(7)
2.029(2)
1.257(12)
1.410(18)
O(4)-C(4)
O(5)-C(4)
O(7)-C(13)
O(8)-Zn#3
O(9)-C(14)
O(10)-C(16)
N(1)-C(7)
N(2)-C(10)
N(3)-C(19)
N(4)-C(23)
1.45(2)
1.53(2)
1.276(13)
2.109(7)
1.452(14)
1.449(13)
1.37(2)
1.21(3)
1.358(14)
1.344(13)
O(5)-C(3)
O(6)-C(7)
O(8)-C(13)
O(9)-C(16)
O(10)-C(15)
O(11)-C(19)
N(1)-C(8)
N(2)-C(11)
N(3)-C(20)
N(4)-C(22)
1.401(17)
1.169(19)
1.226(12)
1.418(16)
1.432(15)
1.225(13)
1.361(17)
1.32(3)
1.390(12)
1.343(13)
N(4)-Zn#4
C(2)-C(3)
C(4)-C(6)
C(8)-C(12)
C(9)-C(10)
C(13)-C(14)
C(16)-C(17)
C(15)-C(19)
C(20)-C(21)
2.095(7)
1.60(2)
1.57(3)
1.43(2)
1.56(3)
1.412(17)
1.477(19)
1.544(15)
1.367(16)
C(1)-C(2)
C(4)-C(5)
C(3)-C(7)
C(8)-C(9)
C(11)-C(12)
C(14)-C(15)
C(16)-C(18)
C(20)-C(24)
C(21)-C(22)
1.40(2)
1.46(3)
1.58(2)
1.44(2)
1.49(3)
1.561(16)
1.51(2)
1.366(17)
1.430(14)
C(23)-C(24) 1.365(15)
O(1)-Zn-N(4)#1
171.5(3)
N(4)#1-Zn-O(8)#2 91.6(3)
N(4)#1-Zn-O(7)
87.3(3)
O(1)-Zn-O(2)
89.0(6)
O(8)#2-Zn-O(2)
92.4(3)
O(1)-Zn-O(3)#3
87.2(4)
O(8)#2-Zn-O(3)#3 175.9(3)
O(2)-Zn-O(3)#3
86.1(3)
O(1)-Zn-O(8)#2
96.6(4)
O(1)-Zn-O(7)
90.8(6)
O(8)#2-Zn-O(7)
87.4(3)
N(4)#1-Zn-O(2) 92.9(4)
O(7)-Zn-O(2)
179.7(3)
N(4)#1-Zn-O(3)#3 84.7(3)
O(7)-Zn-O(3)#3
94.1(3)
Zn#2-O(1)-Zn#3 119.40(17)
S14
Zn#2-O(1)-Zn
C(1)-O(2)-Zn
C(2)-O(4)-C(4)
C(13)-O(7)-Zn
C(16)-O(9)-C(14)
C(7)-N(1)-C(8)
C(19)-N(3)-C(20)
C(23)-N(4)-Zn#4
119.40(17)
124.9(8)
110.6(15)
126.2(8)
109.9(8)
125.4(13)
126.3(9)
119.6(6)
Zn#3-O(1)-Zn
119.40(17)
C(1)-O(3)-Zn#2 134.5(7)
C(3)-O(5)-C(4)
108.4(14)
C(13)-O(8)-Zn#3 127.8(6)
C(15)-O(10)-C(16) 110.0(10)
C(10)-N(2)-C(11) 123.2(19)
C(23)-N(4)-C(22) 115.6(7)
C(22)-N(4)-Zn#4 124.6(6)
O(2)-C(1)-O(3)
O(3)-C(1)-C(2)
C(1)-C(2)-C(3)
C(5)-C(4)-O(4)
O(4)-C(4)-O(5)
O(4)-C(4)-C(6)
O(5)-C(3)-C(7)
C(7)-C(3)-C(2)
O(6)-C(7)-C(3)
N(1)-C(8)-C(12)
126.2(13)
118.7(12)
111.8(12)
115(2)
103.9(16)
109.9(17)
105.4(11)
117.4(14)
121.4(19)
116.9(12)
O(2)-C(1)-C(2)
C(1)-C(2)-O(4)
O(4)-C(2)-C(3)
C(5)-C(4)-O(5)
C(5)-C(4)-C(6)
O(5)-C(4)-C(6)
O(5)-C(3)-C(2)
O(6)-C(7)-N(1)
N(1)-C(7)-C(3)
N(1)-C(8)-C(9)
C(12)-C(8)-C(9)
N(2)-C(10)-C(9)
C(8)-C(12)-C(11)
O(8)-C(13)-C(14)
C(13)-C(14)-O(9)
O(9)-C(14)-C(15)
O(9)-C(16)-O(10)
O(9)-C(16)-C(18)
O(10)-C(16)-C(18)
120.1(14)
127.7(19)
120.0(18)
115.6(10)
115.9(9)
99.1(10)
104.3(9)
109.8(13)
111.2(13)
C(8)-C(9)-C(10) 110.4(19)
N(2)-C(11)-C(12) 118(2)
O(8)-C(13)-O(7) 129.4(12)
O(7)-C(13)-C(14) 115.0(10)
C(13)-C(14)-C(15) 111.2(9)
O(9)-C(16)-C(17) 108.7(11)
C(17)-C(16)-O(10) 110.1(12)
C(17)-C(16)-C(18) 112.3(14)
O(10)-C(15)-C(19) 108.4(9)
O(10)-C(15)-C(14)
O(11)-C(19)-N(3)
N(3)-C(19)-C(15)
C(24)-C(20)-N(3)
C(20)-C(21)-C(22)
N(4)-C(23)-C(24)
104.0(9)
125.8(10)
113.5(9)
115.9(9)
118.4(9)
125.5(10)
C(19)-C(15)-C(14) 115.0(10)
O(11)-C(19)-C(15) 120.6(10)
C(24)-C(20)-C(21) 119.5(8)
C(21)-C(20)-N(3) 124.6(10)
N(4)-C(22)-C(21) 122.3(9)
C(20)-C(24)-C(23) 118.3(11)
115.1(11)
116.1(15)
101.1(12)
104.8(16)
115(2)
106.7(15)
105.2(12)
127.0(17)
111.6(13)
123.0(15)
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
34(1)
34(4)
64(5)
46(1)
34(4)
64(5)
157(1)
270(20)
185(9)
-28(1)
0
-41(5)
-17(1)
0
-18(5)
27(1)
17(2)
43(4)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
O(1W)
63(4)
146(11)
132(9)
100(8)
50(5)
45(4)
41(4)
45(4)
39(4)
350(50)
44(4)
183(14)
89(7)
67(6)
90(6)
32(3)
78(5)
84(6)
37(4)
250(40)
170(8)
165(10)
163(10)
204(12)
190(9)
167(7)
133(7)
151(8)
201(8)
260(40)
4(4)
4(10)
-5(6)
19(7)
-62(6)
4(4)
17(5)
15(5)
8(4)
-20(30)
38(5)
34(9)
4(8)
31(8)
-48(5)
-35(4)
-1(4)
6(5)
2(5)
-50(30)
24(3)
127(11)
59(7)
12(6)
51(5)
15(3)
28(4)
27(4)
19(3)
260(40)
O(2W)
O(3W)
O(4W)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
170(40)
300(40)
190(20)
84(8)
122(13)
30(4)
25(3)
48(6)
78(9)
130(30)
190(30)
137(19)
50(5)
55(8)
35(4)
46(5)
59(7)
106(11)
1230(150)
350(40)
560(50)
185(11)
310(30)
157(8)
151(8)
141(11)
169(15)
60(30)
110(30)
-80(20)
25(6)
-17(11)
7(5)
-37(5)
-17(7)
-40(11)
120(60)
54(13)
-120(30)
29(8)
-10(16)
-4(4)
-14(4)
17(6)
-5(10)
80(20)
93(14)
123(18)
32(5)
40(9)
10(3)
16(3)
30(5)
54(9)
C(4)
C(3)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
113(13)
86(8)
240(30)
190(20)
120(14)
76(8)
139(15)
170(20)
160(20)
101(13)
52(7)
440(60)
143(18)
73(9)
57(7)
47(7)
66(11)
160(20)
200(18)
142(12)
330(40)
270(30)
141(13)
173(14)
250(20)
250(30)
250(30)
30(13)
14(7)
230(40)
-70(19)
5(9)
7(8)
22(10)
7(14)
-90(20)
15(13)
33(8)
170(30)
10(20)
23(11)
-6(9)
-28(14)
-10(20)
-70(20)
61(11)
29(6)
280(40)
107(18)
29(10)
35(6)
42(9)
45(14)
110(20)
Zn
O(1)
O(2)
S16
C(12)
C(13)
C(14)
C(16)
C(15)
C(17)
C(18)
C(19)
129(15)
57(7)
45(6)
38(5)
39(5)
53(8)
166(19)
48(6)
70(9)
56(6)
56(6)
84(8)
56(6)
111(12)
133(16)
57(7)
200(20)
114(9)
166(12)
136(11)
130(10)
198(16)
178(17)
149(10)
-6(10)
-8(6)
3(7)
6(8)
2(6)
-30(11)
34(13)
-4(6)
-12(13)
-11(6)
3(6)
-11(6)
1(5)
-21(9)
1(14)
-7(6)
53(10)
42(5)
31(5)
26(6)
24(4)
14(8)
90(15)
29(5)
C(20)
C(21)
C(22)
C(23)
C(24)
38(5)
40(5)
30(5)
43(5)
34(5)
42(5)
85(8)
46(6)
46(6)
56(6)
132(9)
141(10)
167(12)
181(12)
186(13)
-24(6)
5(7)
-17(6)
-40(7)
-35(7)
-15(5)
6(6)
-4(6)
-17(6)
-9(6)
9(4)
47(6)
16(4)
21(5)
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
No. of ions per secondary building unit [Zn3(O)(1-H)6]2-.
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.
Figure S2.
Structure of the trinuclear secondary building unit [Zn3(3-O)(1-
H)6]2- 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.
S19
Figure S7. Circular dichroism (CD) spectra for (a) optically pure [-Ru(2,2’bipy)3] L-tartarate, (b) Ru(2,2’-bipy)32+ included L-POST-1, (c) Ru(2,2’-bipy) 32+
adsorbed on a simple 3:1 mixture of Ligand D-1 and zinc nitrate, (d) Ru(2,2’bipy) 32+ included D-POST-1.
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 Nalkylated 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 HexylPOST-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) HexylPOST-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 I3with PF6-.
Figure S14. IR spectra of Methyl-POST-1 showing exchange of counterion PF6with 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
S20
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 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-1propanol (solid circle), neopentanol (solid triangle), and 3,3,3-triphenyl-1propanol (+) (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.
S21