tal-organic framework truncated trigonal prismatic tubular ... · truncated trigonal prismatic...
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<Electronic Supplementary Information>
Truncated trigonal prismatic tubular crystals consisting of zeolite L-mimic me
tal-organic framework
Tae Hwan Noh, Jaeseong Jang, Woosik Hong, Haeri Lee and Ok-Sang Jung*
Department of Chemistry, Pusan National University, Pusan 609-735, Korea
Experimental section
Materials and measurements. All chemicals including nickel(II) chloride hexahydrate (Ni
Cl2∙6H2O) and silver(I) nitrate (AgNO3) were purchased from Aldrich, and used without further
purification. K2[L]1-3 (L = bis(methylthio)methylenepropanedioate) was prepared according to th
e procedures outlined in the literature. Elemental microanalyses (C, H, N) were performed on cry
stalline samples by KBSI Pusan Center using a Vario-EL III analyzer. Thermal analyses were pe
rformed under N2 at a scan rate of 10 C/min using a Labsys TGA-DSC 1600. Infrared spectra w
ere obtained on a Nicolet 380 FT-IR spectrophotometer using samples prepared as KBr pellets. 1
H NMR (300 MHz) spectra were recorded on a Varian Mercury Plus 300. Scanning electron mic
roscopy (SEM) images were obtained on a Tescan VEGA 3. Ultra high resolution field emission
scanning electron microscope (UHR-FE-SEM) images were obtained by Hitachi S-4800 at KBSI
Daegu Center. Powder X-ray diffraction data were recorded on a Rigaku RINT/DMAX-2500 dif
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2014
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fractometer at 40 kV, 126 mA for Cu K. Absorption and photoluminescence (PL) spectra were
acquired on an UV-1800 (Shimadzu) and a FluoroMate FS-2 spectrofluorometer (Hitachi), respe
ctively, using a 1 cm quartz cuvette. All optical and fluorescence microscopy images were obtain
ed using an Olympus BX51 microscope equipped with an AxioCam MRc 5 digital camera and U
-MWU2 filter set for red emission.
Synthesis of [K2Ni(L)2(H2O)3(CH3OH)2]. An ethanol solution (3 mL) of NiCl2∙6H2O (24
mg, 0.1 mmol) was carefully layered onto a mixed H2O/methanol solution (4 mL, v/v = 1:10) of
K2[L] (62.5 mg, 0.2 mmol) to obtain single crystals suitable for X-ray single crystallography in 3
days in an 88% yield (59 mg). mp 245 °C (dec.). Found: C, 25.20; H, 3.91. Calc. for C14H26O13S4
K2Ni: C, 25.19; H, 3.93%. νmax/cm1 3525, 3379, 3055, 2931, 1605, 1558, 1396, 1358, 903, 779,
760 and 586. δH(300 MHz; D2O; Me4Si) 2.35 (3 H, s, SCH3).
Synthesis of [Ag4Ni(L)3]∙3.5H2O. Method 1. A methanol solution (15 mL) of AgNO3 (6.7
mg, 0.04 mmol) was layered onto an aqueous solution (20 mL) of [K2Ni(L)2(H2O)3(CH3OH)2] (2
5.5 g, 0.04 mmol). After 1 h, pale green crystalline samples of trigonal rods started to form on th
e bottom of the badge. After 2 days, the crystals were grown to produce trigonal prism shape cry
stals with the average length of 250 µm. Finally, after 4 days, the crystals with a length ranging f
rom 500 to 600 µm were collected by the filtration in a 67% yield based on Ag(I) ions (9.9 mg).
Method 2. A mixture of AgNO3 (16.9 mg, 0.1 mmol), Ni(NO3)2 (14.5 mg, 0.05 mmol), and
K2[L] (42.7 mg, 0.15 mmol) in H2O (30 mL) was stirred for 10 min at room temperature, and the
n methanol was layered onto the solution to yield the truncated trigonal tubular crystals. Yield, 3
6.7 mg (52% based on Ag(I) ions). mp 175 °C (dec). Found: C, 18.47; H, 2.12. Calc. for C18H25
O15.5S6NiAg4: C, 18.45; H, 2.15%. νmax/cm1 3535, 3365, 3234, 3051, 2928, 1603, 1558, 1396, 1
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356, 901, 775, 754 and 580. δH(300 MHz; D2O; Me4Si) 2.39 ppm (6 H, s, SCH3).
The crystalline solids of [Ag4Ni(L)3]∙3.5H2O are very stable under the ambient conditions, a
nd insoluble in water and other common organic solvents including acetonitrile, dimethyl sulfoxi
de, and N,N-dimethylformamide.
Procedure for the reduction of p-nitrophenol into p-aminophenol. An aqueous solution o
f NaBH4 (1.5 mL, 1 mM) was mixed with p-nitrophenol (1.5 mL, 50 µM) in a standard quartz cu
vette. The light-yellow color of the p-nitrophenol turned to yellowish-green, owing to the formati
on of p-nitrophenolate ion. 5 mg of ZLMOF or Ag(0)/ZLMOF was added to the solution and the r
esulting solution was sonicated for 5 min at room temperature. The yellow color of the solution v
anished, indicating the reduction of p-nitrophenol.
X-ray crystal structure determinations. X-ray data were collected on a Bruker SMART au
tomatic diffractometer with graphite-monochromated Mo Ka radiation (λ = 0.71073 Å) and a CC
D detector at 25 °C. Thirty-six frames of two-dimensional diffraction images were collected an
d processed to obtain the cell parameters and orientation matrix. The data were corrected for Lor
entz and polarization effects. The absorption effects were corrected using the multi-scan method
(SADABS).4 The structures were solved using the direct method (SHELXS 97) and refined by fu
ll-matrix least squares techniques (SHELXL 97).5 The non-hydrogen atoms were refined anisotro
pically, and the hydrogen atoms were placed in calculated positions and refined only for the isotr
opic thermal factors. For [Ag4Ni(L)3]∙3.5H2O, the hydrogen atoms of O(5) atom were not introdu
ced in the mother atom, owing to the O(5) atom is located on the special position (both C3-axis a
nd inversion center). The crystal parameters and procedural information corresponding to the dat
a collection and structure refinement are listed in Table S2.
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References for the Experimental section
1 T. H. Noh, Y.-A. Lee and O.-S. Jung, Eur. J. Inorg. Chem., 2010, 132-140.
2 N. Katagiri, S. Ise, N. Watanabe and C. Kaneko, Chem. Pharm. Bull., 1990, 38, 3242-3248
.
3 T. Kosakada, K. Taninaka and H. Kurono, Jpn. Pat., 78 03519, 1978.
4 G. M. Sheldrick, SADABS: A program for Empirical Absorption Correction of Area Detec
tor Data, University of Göttingen, Germany, 1996.
5 (a) G. M. Sheldrick, SHELXS-97: A Program for Structure Determination, University of G
öttingen, Göttingen, Germany, 1997; (b) G. M. Sheldrick, SHELXS-97: A Program for Str
ucture Determination, University of Göttingen, Göttingen, Germany, 1997.
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Aperture
Pitch
Width
Table S1 Comparison of ZLMOF with Zeolite L
[Ag4Ni(L)3]∙3.5H2O Zeolite La
Rhombohedral Crystal system Hexagonal
P3 Space group P6/mmm
15.8928(3) a = b (Å) 18.126
7.9116(1) c (Å) 7.567
1730.60(5) Volume (Å3) 2153.11
2.247 Density (g cm3) 2.11
7.912(1) Pitch (Å) 7.5
11.968(1) Width (Å) 12.6
7.55 Aperture (Å) 7.1aSee Ref [2] in the context.
Aperture
Pitc
h
Width
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Table S2 Crystal Data and Structural Refinements for [K2Ni(L)2(H2O)3(CH3OH)2] and [Ag4Ni(L
)3]∙3.5H2O
[K2Ni(L)2(H2O)3(CH3OH)2] [Ag4Ni(L)3]∙3.5H2O
Formula C14H26O13S4K2Ni 2 C18H24O15.5S6NiAg4
Mw 667.50 2341.84Crystal system Triclinic TrigonalSpace group P1 P3a (Å) 7.3428(2) 15.8928(3)b (Å) 13.2262(3) 15.8928(3)c (Å) 13.8832(3) 7.9116(1)α (°) 89.836(1) 90β (°) 83.498(1) 90γ (°) 77.413(1) 120V (Å3) 1307.10(5) 1730.60(5)σ (Mg m3) 1.696 2.247Z 2 1µ (mm1) 1.438 3.181F(000) 688 1136Rint 0.0285 0.0995Data / restraints / parameters 5398 / 0 / 307 2658 / 0 / 150Completeness (%) 99.5 (θ = 26.5°) 100 (θ = 27.5°)GoF on F2 1.025 1.015R1 (I > 2σ(I))a 0.0376 0.0715wR2 (all data)b 0.1008 0.2386
aR1 = Σ||Fo| |Fc||/Σ|Fo|, bwR2 = (Σ[w(Fo2 Fc
2)2]/Σ[w(Fo2)2])1/2
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Fig. S1 (a) ORTEP drawings of [K2Ni(L)2(H2O)3(CH3OH)2]. The hydrogen atoms and solvate w
ater and methanol molecules were omitted for clarity. (b) Coordinating nature around the two kin
ds of potassium(I) ions and (c) packing diagram.
ONi
O
O
OOO
O OK
O
OO
O
H3COH
OO
ONi
O
O
OOO
O OK
O
OO
O
H3COH
H2O
(b)
ac
b
(c)
(a)
Ni1
O1O2
O3 O4
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S1
S4
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O5O6
O7
O8
O9
O10
K1
K2
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Fig. S2 Top: TGA (red) and DSC (blue) curves of ZLMOF. Bottom: SEM image of residue of [
Ag4Ni(L)3]∙3.5H2O after calcination at 800 °C for 3 h. Inset: powder XRD pattern for Ag(0)/NiO
residue (white line). Red and green lines represent the reference pattern of Ag(0) and NiO, respect
ively, from the ICDD database (PDF no. 04-0783 and 04-0835, respectively). Bar = 20 μm.
2θ (°)
40 60 80
200 400 600 800
80
100
120
200 400 600 800
80
100
120
Temperature (°C)
Wei
ght l
oss (
%)
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Fig. S3 Powder XRD patterns for (red line) [K2Ni(L)2(H2O)3(CH3OH)2] along with (black line) t
he simulated pattern from single-crystal X-ray diffraction data.
10 20 30 40 50 60
2θ (°)
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Fig. S4 Top view of the schematic drawing of ZLMOF along with the tectonic units. Green and
gray spheres denote the central nickel(II) and silver(I) metal ions, respectively.
O
OO
OS Ag
AgS
O
OO
OS
SNi
O
O
O
ONi
O
O
O
O
≡
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Fig. S5 Highlighted side view for coordination nature around two-coordinated silver(I) ions. Eac
h silver(I) ion has an occupancy of 1/3. Green, Ni; grey, Ag; yellow, S; red, O; white, C and H.
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Fig. S6 Space-filling diagrams (top view, left; side view, right) for (H2O)13 clusters of (a) ZLMO
F and (b) {[Ni6(N3)12L6]∙13H2O}∞ (HL = 2-carboxymethylmercapto-1,3,4-thiadiazole acid, see
Ref [11] in the context). (H2O)7 clusters as core parts are highlighted for clarity.
(a)
(b)
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Fig. S7 Size distribution of truncated trigonal rods and tubular morphologies for (a) 1 d, (b) 2 d,
and (c) 4 d.
0 40 80 120 160
0 40 80 120 160
Length (µm)
(a)
50 100 150 200 250
50 100 150 200 250
Length (µm)
(b)
140 210 280 350
140 210 280 350
Length (µm)
(c)
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Fig. S8 SEM image of ZLMOF after 4 d. Scale bar = 30 μm.
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Fig. S9 SEM image of ZLMOF obtained from a mixed water/methanol/acetone solution. Scale b
ar = 30 μm.
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Fig. S10 (a) Optical microscopy and (b) scanning electron microscopy images of the truncated pr
ism-shaped tube penetrated by a cotton thread. (c) The cotton thread-penetrated tube was cut wit
h a razor blade. White bar, 200 µm; black bar, 20 µm.
(a) (b)
(c)
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Fig. S11 Plot representing the aspect ratio for the (red triangles) truncated trigonal rods and (blue
squares) tubular morphologies of ZLMOF.
100 200 300 400 500 600 7000
20
40
60
80
100
120
Length (µm)
Wid
th (µ
m)
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Fig. S12 Powder XRD patterns of ZLMOF: (a) prismatic rods and (b) tubular morphologies.
road
10 20 30 40 50 60 70
tube
2θ (°)
(a)
(b)
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Fig. S13 (a-d) IR spectra of evacuated ZLMOF, [Ag4Ni(L)3], showing the re-incorporation of wa
ter by exposure to air for (b) 5 min, (c) 10 min, and (d) 30 min. (e) designates the IR spectrum of
as-prepared ZLMOF.
Vacuum
Wavenumber (cm1)
%Tr
ansm
ittan
ce
4000 3500 3000 2500
4000 3500 3000 2500
(a)
(b)
(c)
(d)
(e)
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Fig. S14 Powder XRD pattern for (blue) the as-synthesized ZLMOF and (red) the re-adsorbed Z
LMOF.
10 20 30 40 50 60
2θ (°)
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Fig. S15 Optical microscopy (left) and fluorescent microscopy images (right) for the cross sectio
n of the crystal of (a) ZLMOF and (b) Ag(0)/ZLMOF.
(a)
(b)
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Fig. S16 TEM image for Ag(0)/ZLMOF showing the silver(0) nanoparticles on the surface. Red a
nd white lines denote powder XRD patterns for Ag(0)/ZLMOF and Ag(0) as references from the I
CDD database (PDF no. 04-0783), respectively.
200 nm200 nm
200 nm
50 nm50 nm
50 nm
20 40 60
Inte
nsity
2θ (°)
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Fig. S17 (a) IR spectra and (b) powder XRD patterns for (blue lines) ZLMOF and (red lines) Ag(
0)/ZLMOF.
(a)
%Tr
ansm
ittan
ceWavenumber (cm1)
tube
4000 3000 2000 1000
tube-Ag
(b)
Inte
nsity
2θ (°)20 40 60
tube-Ag
original