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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

S2

S1

S4

S3

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