Soft Matter

Cite this: Soft Matter, 2012, 8, 6557 www.rsc.org/softmatter

View Article Online / Journal Homepage / Table of Contents for this issue

Dynamic Article Links <

PAPER

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.

A tetrazole-based metallogel induced with Ag+ ion and its silver nanoparticle in catalysis
Ji Ha Lee,a Sunwoo Kang,b Jin Yong Lee*b and Jong Hwa Jung*a
Received 11th February 2012, Accepted 23rd April 2012 DOI: 10.1039/c2sm25316j A tetrazole-based ligand forms a supramolecular metallogel in the presence of Ag+ in aqueous solution at basic condition. The silver-induced metallogel has been characterized by SEM, TEM, XRD and rheometry. The metallogel exhibits a ber structure. Upon standing, silver nanoparticles grow in the gel. TEM conrmed that the particles are exclusively formed in the gel bers. The size of the silver nanoparticles formed on the gel bers is dependent to the concentration of silver during gel formation. The silver nanoparticles show a face-centered cubic crystalline structure. The silver nanoparticles can effectively catalyze reduction of 4-nitrophenol by sodium borohydride in aqueous solution. The formation of Ag+-induced metallogels does not strongly depend on anions. According to DFT calculations, two silver cations are coordinated to nitrogen at the tetrazole moiety. The other silver cation is coordinated to the nitrogen of the pyridine and coordinated to the oxygen of the amide moiety. Furthermore, the rheological properties of the Ag+-tetrazole-based metallogel were strongly dependent on the concentration of AgClO4.

Introduction
Organogels and hydrogels composed from small molecules or low molecular weight gelators (LMWGs), which are linked into bers by supramolecular interactions, are current topics of great interest. Supramolecular gels have been studied as soft materials for applications in drug-delivery systems, tissue engineering, sensing devices, separation and optoelectronic devices.117 The incorporation of labile metals or anions within these supramolecular gels is of particular interest because metallogel structures are applicable in various processes such as redox responsiveness,18,19 catalytic action,20,21 absorption,22,23 emission,2426 magnetism23 and electron emission.21 In addition, the metallogels composed of a coordination polymer network structure can be rapidly, efciently and easily prepared under mild conditions in comparison to typical crystalline coordination polymer materials like metalorganic frameworks (MOFs), which display similar properties.27 Tetrazole derivatives, with multiple binding sites, promote cross-linking to form a polymer network, a condition that is critical for gelation.28 We have undertaken the investigation of nanomaterials that combine tetrazole and pyridyl groups.2830

a Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, Korea. E-mail: jonghwa@gnu.ac.kr b Department of Chemistry and Institute of Basic Science Sungkyunkwan University, Suwon 440-746, Korea. E-mail: jinylee@skku.edu Electronic Supplementary Information (ESI) available: Measurement data. See DOI: 10.1039/c2sm25316j/

Recent investigations have focused on the templation of metallic and semiconductor nanoparticles using a gel network that functions not only as a coordinating substrate for preprepared nanoparticles,31,32 but also serves as the medium that directs the in situ synthesis of the nanosized materials.3339 In particular, metallic silver nanoparticles are of interest because of their optical and antibacterial properties,4045 and a variety of novel synthesis media and techniques have been developed to control their size and shape. In addition, silver nanoparticles supported within the nanostructures are of special interest due to their stability, high efciency, and lack of reactivity with other reactants.4547 For example, Steed et al. reported on the rheological properties and silver nanoparticle formation in a pyridine-based metallogel with AgBF4.47 The sizes of silver nanoparticles produced from the metallogel in the presence of AgBF4 are dependent on the concentration of silver ions. The silver nanoparticles in the presence of 2 and 3 equivalents of silver ions gave a broadened size distribution ranging from 5 to 50 nm. The rheological properties of the silver metallogel are dependent on the concentration of silver. This is the rst example of silver nanoparticle formation in a metallogel with silver ions. With this in mind, the tetrazole moiety was chosen as the framework for the attachment of ligands because this material has been well-dened and extensively developed in coordination polymer chemistry.48 Herein, we report the formation of a metallogel of the tetrazole-based ligand (1) containing Ag+ ions and we have examined the rheological properties of the metallogels at different concentrations of Ag+. The diameter and size distribution of the silver nanoparticles was nely controlled from the tetrazole-based metallogel in the presence of silver ions.
Soft Matter, 2012, 8, 65576563 | 6557

This journal is The Royal Society of Chemistry 2012

View Article Online

The rheology of the metallogel strongly depends on the concentration of Ag+. Furthermore, the silver nanoparticles formed on the gel bers can effectively catalyze reduction of 4nitrophenol by sodium borohydride in aqueous solution.

concentrations from 1.0 to 5.0 equivalents with respect to the ligand concentration. The volume of the metal salt solution was typically around 1.0 wt% of the total solution. Catalytic reduction of 4-nitrophenol

Experimental
Instruments
Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.
1 H and 13C NMR spectra were measured on a Bruker ARX 300 apparatus. IR spectra were obtained for KBr pellets, over the range 4004000 cm1, with a Shimadzu FT-IR 8400S instrument, and mass spectra were obtained by a JEOL JMS-700 mass spectrometer. The optical absorption spectra of the samples were obtained using a UVvis spectrophotometer (Hitachi U-2900). All uorescence spectra were recorded with RF-5301PC spectrophotometer.

In a typical experiment, 2.5 ml of water, 0.0750 ml of aqueous NaBH4 (5.0 mM), and 0.150 ml of 0.05 mM 4-nitrophenol were mixed in a standard quartz cuvette. Then, 0.010 ml of the gel 1 with Ag+ (2.0 equivalents) was introduced into the solution and time-dependent absorption spectra were recorded every 30 s over the range 1901000 nm at 25  C. Furthermore, the column packed with silver nanoparticlegel ber composite materials was prepared in a syringe (10 0.5 cm). The catalytic capacity was tested with rate 0.60 mL cm2 s1. Compound 2 Thionyl chloride (5.9 g, 50 mmol) was added dropwise to compound 4 (7.4 g, 50 mmol) and triethylamine (5.1 g, 50 mmol) in THF. The mixture was reuxed for 2 h and cooled to room temperature to allow formation of compound 3. Then, to the solution of 3 in CHCl3 was added dropwise an acetonitrile solution of 2,5-diaminopyridine (2.7 g, 25 mmol) and triethylamine (5.1 g, 50 mmol), with cooling by a salt and ice water bath. The solution was stirred for 12 h, and then water was added. From the resulting solution, a yellow powder was ltered and washed with a dilute Na2CO3 solution, distilled water, and then a small amount of cold methanol. The compound 2 was obtained as yellowish white powder (5.4 g, 59%). 1H NMR (300 MHz, DMSO-d6) 10.35 (s, 2H, NH), 8.09 (d, 2J(H,H) 8.4 Hz, 4H; ArH), 8.02 (d, 2J(H, H) 8.4 Hz, 4H; ArH), 7.75 (d, 2J(H,H) 8.1 Hz, 1H, ArH), 7.68 (d, 2J(H,H) 8.1 Hz, 1H, ArH), 6.10 (s, 1H, ArH) 13C NMR (DMSO-d6) d 165, 152, 139, 135, 132, 128, 123, 119, 111 ppm. IR (KBr, cm1):3369, 3314, 3178, 3050, 2230, 1698, 1643, 1537, 1506, 1396, 1311, 1250, 1140, 1024, 893, 857, 823, 762, 666, 636, 566, 526. HRMS (FAB+) m/z 368.1069[(M + H)+calcd for C2H13N5O2: 368.1574]. Anal.calcd for C2H13N5O2: C, 68.71; H, 4.32; N, 19.43. found: C, 68.66; H, 3.57; N,19.06. Compound 1 A mixture of compound 2 (1 g, 27 mmol), NaN3(2.123 g, 330 mmol) and triethylamine hydrochloride (4.496 g, 330 mmol) in 100 ml of toluene and 10 ml of methanol was heated at reux for 4 days. The precipitate was then collected by hot ltration and dissolved in aqueous NaOH (1 M). The resulting clear, colorless solution was titrated with HCl (1 M) until the pH of the solution was 4. The ensuing white precipitate was washed with successive aliquots of distilled water and diethyl ether to afford 0.5 g (41.7%) of product. 1H NMR (300 MHz, DMSO-d6) 10.29 (s, 2H, NH), 8.18 (d, 2J(H,H) 8.4 Hz, 4H; ArH), 8.15 (d, 2J(H,H) 8.4 Hz, 4H; ArH), 7.84 (d, 2J(H,H) 8.1 Hz, 1H, ArH), 7.81 (d, 2J(H, H) 8.1 Hz, 1H, ArH), 6.6 (s, 1H, ArH) 13C NMR (DMSO-d6) d 165, 155, 150, 140, 132, 122, 121, 111, 110 ppm. IR (KBr, cm1):3449, 3240, 3061, 2856, 2755, 2720, 2649, 2498, 1698, 1643, 1552, 1486, 1441, 1361, 1285, 1144, 1104, 1014, 853, 827, 732, 676, 525, 440. HRMS (FAB+) m/z 454.1410 [(M + H)+calcd for C2H15N11O2:454.2013]. Anal. calcd for C2H15N11O2: C, 56.02; H, 3.38; N, 34.03. found: C, 55.63; H, 3.33; N,33.98.
This journal is The Royal Society of Chemistry 2012

Preparation TEM and SEM observations For transmission electron microscopy (TEM), a piece of the metallogel was placed on a carbon-coated copper grid (400 mesh) and removed after 1 min, leaving some small patches of the sample on the grid. The specimens were examined with a JEOL JEM-2010 transmission electron microscope operating at 200 kV using an accelerating voltage of 100 kV and a 16 mm working distance. Scanning electron micrographs of the samples were taken with a eld emission scanning electron microscope (FESEM, Philips XL30 S FEG). The accelerating voltage of SEM was 515 kV and the emission current was 10 mA. Rheological measurements The rheological properties were observed on freshly prepared metallogels using a controlled stress rheometer (AR-2000ex, TA Instruments Ltd, New Castle, DE, USA). A cone type geometry of 40 mm diameter was employed throughout. Dynamic oscillatory work kept a frequency of 1.0 rad s1. The following tests were performed: increasing the amplitude of oscillation up to 100% apparent strain on shear, time and frequency sweeps at 25  C (60 min and from 0.1100 rad s1, respectively). Unidirectional shear routines were performed at 25  C covering a shear-rate regime between 101 and 103 s1. Mechanical spectroscopy routines were completed with transient measurements. In doing so, the desired stress was applied instantaneously to the sample and the angular displacement was monitored for 60 min (retardation curve). Photophysical studies UV-Vis absorption and emission spectra of the metallogel were observed at room temperature and in the range 200800nm. The absorption properties of metallogel 1 were studied extensively. UV-Vis absorption spectra of metallogel 1 (20 mM) were observed in the presence of Ag+ (2.05.0 equiv). Gelation test Metallogels were prepared by dissolving 1.0 weight percent in aqueous solution at different pH values. To this solution a small volume of metal ions in aqueous solution was added in varying
6558 | Soft Matter, 2012, 8, 65576563

View Article Online

Results and discussion

Ligand 1 containing two tetrazole moiteties as a binding site for silver ion was conveniently prepared by a two step reaction according to methods described previously (Scheme 1). The reaction of 2,5-diaminopyridine with isocyanobenzoic chloride in the presence of triethylamine gave p-substituent cyano compound 2 in THF, in which the cyano groups can be easily changed into tetrazole groups by simple reaction. Then, compound 2 was reacted with sodium azide in the presence of triethylammonium chloride to give the desired product 1 in toluene and methanol, as conrmed by 1H, 13C NMR, mass spectroscopy and elemental analysis. For gelation studies, samples of 1 were prepared by dissolving the compound (1% by weight) in water in aqueous solution at different pH values. The ligand solution was then mixed with aqueous silver perchlorate. Interestingly, ligand 1 in the presence of greater than 2.0 equivalents of AgClO4 was found to gel under basic conditions (Fig. 1A and 1B) whereas silver complexes of ligand 1 did not form gels under acidic and neutral conditions (Fig. 1A:a and b), because the nitrogen atoms of the tetrazoles would be protonated under acidic conditions. In addition, ligand 1 has low solubility under neutral conditions, which may also inhibit gel formation. Although the metallogel with AgClO4 (2.0 equivalents) appeared very robust and homogeneous in basic conditions, it was not thermoreversible as observed by the inverted test tube method due to the poor solubility of the ligandsilver aggregates. After formation of the metallogel, the color of the metallogel with Ag+ was white at the initial stage in the dark, and then it gradually changed to brown coloration over time due to reduction by NaOH and formation of metallic silver nanoparticles. With increasing Ag+ concentration, the color of the metallogel turned more intensely brown due to the formation of a greater number of silver particles. In addition, 1 could be gelated with a variety of silver counter ions such as NO3 and ClO4 (ESI, Fig. S1), but 1 could not gelate when the silver counter ion was CH3COO or SO42 (ESI, Fig. S1) because the Hofmeister effect of CH3COO or SO42 is much larger than those of ClO4 and NO3. The large Hofmeister effect of anions induces the solid products, due to low solubility in water. Also, CH3COO or SO42 would be coordinated to the silver ion. Therefore, they did not form the gel. These variable results indicate that the dependence of metallogel formation of 1 may be attributed to different coordination properties of anions.

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.

Fig. 1 (A) Photograph of gels 1 with AgClO4 (2.0 equiv) at (a) pH 2, (b) pH 7 and (c) pH 10. (B) Photograph of 1 with AgClO4 (a) 1.0 equiv, (b) 2.0 equiv, (c) 3.0 equiv, (d) 4.0 equiv and (e) 5.0 equiv at pH 10.

The morphology of metallogel 1 with AgClO4 (2.0 equivalent) in aqueous solution with basic conditions exhibited a ber structure of 2050 nm diameter and several mm in length (Fig. 2). The morphology of xerogels obtained in the presence of Ag+ with different anions was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Based on SEM images, the use of other counter ions of Ag+ that successfully formed metallogel 1 had a negligible effect, producing a similar nanober structure with diameters of 3050 nm (ESI, Fig. S2). The presence of silver nanoparticles was further conrmed by transmission electron microscopy (TEM) for samples after 1 day on the bench. Samples were dispersed in ethanol. For a metallogel 1 with 2.0 equivalent of AgClO4, the TEM image showed spherical particles exclusively attached to the metallogel bers (Fig. 3A; a). The size distribution of these particles varied from 13 nm (Fig. 3A; a). As expected from the deeper color of the metallogels with higher concentrations of the silver salt, samples containing 3.0 and 4.0 equivalents of AgClO4 showed larger nanoparticles accompanied by a size distribution ranging from 1.5 to 3.5 nm

Fig. 2 SEM image of gel 1 with AgClO4 (2.0 equiv) in water.

Scheme 1 Synthetic route of ligand 1.

This journal is The Royal Society of Chemistry 2012

Soft Matter, 2012, 8, 65576563 | 6559

View Article Online

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.

Fig. 4 Powder XRD patterns of gel 1 with Ag+ (2.0 equiv) (a) at initial stage and (b) after 1 day.

Fig. 3 (A) TEM images of gels 1 with Ag+ (a) 2.0 equiv, (b) 3.0 equiv, (c) 4.0 equiv and (d) 5.0 equiv. (B) Ag+ the size distributions of Ag nanoparticles obtained from (a) 2.0 equiv, (b) 3.0 equiv, (c) 4.0 equiv and (d) 5.0 equiv.

(Fig. 3A; b and c and 3B; b and c) and at the highest concentration even up to 2.05.0 nm (Fig. 3A; d and 3B; d). The size and distribution of the silver nanoparticles formed in the work were relatively smaller and narrower compared to previous reported methods.47 In addition, high resolution TEM images revealed lattice domains in all particles (ESI, Fig. S3), indicating that particles had a crystalline structure. An energy dispersive X-ray (EDX) spectrum of the same area conrmed the presence of silver in the particles (ESI, Fig. S4). To conrm a more detailed crystalline structure of the silver nanoparticle, the XRD pattern of metallogel with AgClO4 (2.0 equivalents) was measured (Fig. 4). There were two different reection patterns of metallogel with Ag+ in the initial stage. The main reection peaks can be indexed to the corresponding (111), (102), (020), (211), (113), (112), (220), (213), (114), (024), (215) and (126) faces at the initial stage, which correspond to the reection of a face-centered cubic (fcc) crystalline AgClO4. In addition, the minor reection peaks exhibited at 38, 44, 64 and 77 q correspond to metallic silver particles. On the other hand, after 24 h, only four reection peaks appeared at 38, 44, 64 and 77 for (111), (200), (220) and (311), respectively. All these distinct diffraction peaks correspond to the reection of face-centered cubic (fcc) crystalline silver without any impurity peaks (JCPDS 65-2871). These results indicated that crystalline AgClO4 was changed into crystalline silver with a typical fcc structure by the reducing agent. The metallogel networks of ligand 1 with Ag+
6560 | Soft Matter, 2012, 8, 65576563

provide an uncomplicated and mild route to the formation of silver nanostructures. The fabrication of nanoparticulate silver in gels both polymeric and supramolecular has been reported previously,47 however the present approach is a rare example where the silver acts both as the gelling agent and as the nanoparticle growth substrate.47 To examine the inuence of the formation of silver nanoparticles in the metallogel with different concentrations of AgClO4, a sample of the metallogel containing Ag nanocrystals was dissolved in DMSO and the UV-vis spectrum of the solution was observed (Fig. 5A). The absorption band of free ligand 1 appeared at 280 nm, whereas the absorption bands of metallogel 1 with AgClO4 (2.0 equivalent) appeared at 270 nm and 380 nm and the absorption band at 380 nm can be assigned as the typical surface plasmon of small size silver nanoparticles. The absorption band of the metallogel appearing at 380 nm was shifted to 450 nm by increased aging time (Fig. 5B), and then the band at 450 nm gradually increased in intensity, because the small silver nanoparticles had grown into larger sized particles resulting in a larger amount of silver particles formed onto the surface of the self-assembled nanorod. On the other hand, the absorption band of the metallogel prepared with a higher concentration of AgClO4 (5.0 equivalent) appeared at 450 nm at the initial stage, which is attributed to a relatively large size distribution of silver particles as compared to those formed with 2.0 equivalent of AgClO4. In addition, we observed the uorescence properties of the metallogel with AgClO4. The free ligand did not display uorescence emission whereas the metallogel with AgClO4 showed a strong emission band at 492 nm (excitation at 270 nm)

Fig. 5 (A) UV-vis spectra of gel 1 upon addition of AgClO4. (B) UV-vis spectra of gel 1 with AgClO4 (2.0 equiv) with increased aging times.

This journal is The Royal Society of Chemistry 2012

View Article Online

at the initial stage (Fig. S5). However, the strong emission of metallogel with AgClO4 was quenched after 1 day on the bench, due to transformation into silver particles. To determine the stoichiometric ratio between 1 and Ag+, we observed the absorption changes of the metallogel 1 upon the addition of different concentrations of Ag+ by UV-vis spectroscopy. The Job plot using the absorption changes indicated 3 : 2 binding for 1 with Ag+ (ESI, Fig. S6). Furthermore, the infrared spectra of dried metallogel 1 in the presence of different concentrations (2.0, 3.0 and 4.0 equivalents) of AgClO4 were recorded and compared to that from the free ligand (ESI, Fig. S7). In the free ligand, peaks corresponding to the C]O and C]N stretches occurred at 1705 and 1650 cm1, respectively, and in the dried metallogel in the presence of 2.0 equivalent of AgClO4 they were shifted to 1654 and 1570 cm1, respectively. Then, the peaks corresponding to the C]O and C]N stretches of dried metallogel with AgClO4 (3.0 and 4.0 equivalent) were shifted to 1600 and 1552 cm1, respectively. The shift of C]N vibration might be due to coordination of Ag+ whereas the shift of C]O vibration might be due to the intermolecular hydrogenbonding interaction. In particular, the vibrational bands of C] O and C]N stretches of the metallogel with 4.0 equivalent of AgClO4 were shifted more than those obtained with 2.0 and 3.0 equivalents of AgClO4, in which the largest amount of free ligand 1 is due to complex formation with AgClO4. To understand the structural features of gel formed in a 1Ag+ complex, we carried out density functional theory (DFT) calculations employing nonlocal density functional of Beckes three parameterized LeeYangParr exchange functional (B3LYP) with a 3-21G* basis set using a suite of Gaussian 09 programs.49 We considered the metallogel structure of 1Ag+, which contains four molecules of ligand 1 and three silver cations. The optimized structure (Fig. 6) illustrates that the silver cations are linearly coordinated to ligand 1. The two silver cations are coordinated to nitrogen at the tetrazole moiety with interatomic N/Ag  The other silver cation is distances in the range 2.1212.169 A. coordinated to the nitrogen of pyridine with a N/Ag distance of  and coordinated to the oxygen of the amide moiety with 2.155 A  The coordinations between ligand 1 Ag/O distance of 2.159 A. and the silver cations have a signicant role in forming a gel structure. In addition, hydrogen bonding between ligand 1 also supports the gel structure. The distances of hydrogen bonding  (N/H) were calculated to be 1.827 and 1.746 A. To gain insight into the thermally promoted stability of the metallogel with Ag+, the transition temperature (Tsolgel) of the metallogel was measured by differential scanning calorimetry (DSC) (ESI, Fig. S8). The metallogel with AgClO4 (2.0 equivalents) showed a sharp endothermic peak at around 76  C, which was attributed to a gel to sol transition.

To study the catalytic activity of silver nanoparticles deposited onto the gel bers prepared from 2.0 equivalents of AgClO4, the reduction of 4-nitrophenol (4-NP) by sodium borohydride (NaBH4) was investigated as a model reaction because this reaction is rapid and can be easily characterized. The catalytic reduction of several aromatic nitro compounds to the corresponding amino derivatives using NaBH4 and metal nanoparticles has been reported.31,32 Nitro compounds are inert to NaBH4 if it is used alone. However, the metal nanoparticles effectively catalyzed the reduction of nitro compounds by acting as an electron relay system; electron transfer from NaBH4 to the nitro compounds occurred through the metal particles. The reaction can be readily monitored with UV-vis spectroscopy. In NaBH4 medium, the peak corresponding to 4-NP at 317 nm was red-shifted to 400 nm because of the formation of 4-nitrophenolate (Fig. 7). The reduction can be visualized by the disappearance of the 400 nm peak with the concomitant appearance of a new peak at 300 nm after the catalysis. This peak has been attributed to 4-aminophenol (4-AP). This result conrmed that the silver nanoparticles deposited onto the gel bers catalyzed the reduction reaction. Furthermore, silver nanoparticles deposited onto the gel ber were immobilized in the glass tube, and its catalytic activity was tested. The passage of the solution containing 4-NP and NaBH4 through the column packed with the silver nanoparticlegel ber composite material at a rate 0.60 mL cm2 s1 resulted in the reduction of greater than 95% of the 4-NP. This result was reproducible over tens of consecutive runs, and the catalytic reaction did not result in undesired system alterations and/or detachment of silver nanoparticles. Rheological information is an indicator of the behavior of the metallogels when they are exposed to mechanical stress, especially the storage (or elastic) modulus G0 , which represents the ability of the deformed material to snap back to its original geometry, and the loss (or viscous) modulus G00 , which represents the tendency of a material to ow under stress. Two rheological criteria required for a metallogel are: (i) the independence of the dynamic elastic modulus, G0 , with respect to the oscillatory frequency and (ii) G0 must exceed the loss modulus G00 by about 1 order of magnitude.

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.

Fig. 6 The optimized structure of a model system of the gel form of 1 Ag+.

Fig. 7 UV-vis spectra of a solution containing 0.05 mM 4-nitrophenol and 5 mM NaBH4 (a) before and (b) after addition of gel 1 with AgClO4. UV-vis spectra of (c) ligand 1 and (d) 4-amionophenol obtained from (a) curve tting.

This journal is The Royal Society of Chemistry 2012

Soft Matter, 2012, 8, 65576563 | 6561

View Article Online

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.

The dynamic strain sweep to determine the proper conditions for the dynamic frequency sweep of the metallogel was studied at different concentrations of Ag+. As shown in Fig. S9, the values of the storage modulus (G0 ) and the loss modulus (G00 ) exhibited a weak dependence from 0.1 to 1.0% of strain (with G0 dominating G00 ), indicating that the sample is a metallogel. The values of both G0 and G00 of the metallogel in the presence of 5.0 equivalents of Ag+ were remarkably enhanced in comparison to the metallogels in the presence of only 2.0 or 3.0 equivalents of Ag+. These results reect the stabilization of the metallogel with almost complete coordination of the polymer structure in the presence of 5.0 equivalents of Ag+. The dynamic frequency sweep to study the metallogel was used after setting the strain amplitude to 0.01% (within the linear response region of the strain amplitude). Fig. S10 illustrates that G0 and G00 are almost constant with the increase of frequency from 0.1 to 100 rad s1. The value of G0 is about 25 time larger than that of G00 over the whole range (0.1100 rad s1), suggesting that the metallogel is fairly tolerant to external force. As observed by changes of dynamic strain sweep, the values of both G0 and G00 of the metallogel at values above 5.0 equivalent of Ag+ concentration were 10 times larger than that of the metallogel in the presence of 2.0 equivalents of Ag+. All values of G0 and G00 in the coordination polymer metallogel are strongly inuenced by the concentration of Ag+ in the ligand 1Ag+ complex.

References
1 G. O. Lloyd and J. W. Steed, Nat. Chem., 2009, 1, 437. 2 R. G. Weiss and P. Terech, Molecular Gels: Materials with SelfAssembled Fibrillar Networks, Springer, Dordrecht, 2006. 3 Z. Yang, P. L. Ho, G. Liang, K. H. Chow, Q. Wang, Y. Cao, Z. Guo and B. Xu, J. Am. Chem. Soc., 2007, 129, 266. 4 S. R. Jadhav, P. K. Vemula, R. Kumar, S. R. Raghavan and G. John, Angew. Chem., Int. Ed., 2010, 49, 1. 5 G. John, B. V. Shankar, S. R. Jadhav and P. K. Vemula, Langmuir, 2010, 26, 17843. 6 P. K. Vemula, J. Li and G. John, J. Am. Chem. Soc., 2006, 128, 8932. 7 F. Zhao, M. L. Ma and B. Xu, Chem. Soc. Rev., 2009, 38, 883. 8 A. Ajayaghosh, V. K. Praveen and C. Vijayakumar, Chem. Soc. Rev., 2008, 37, 109. 9 T. H. Kim, M. S. Choi, B. H. Sohn, S. Y. Park, W. S. Lyoo and T. S. Lee, Chem. Commun., 2008, 2364. 10 P. Terech and R. G. Weiss, Chem. Rev., 1997, 97, 3133. 11 T. Ishi-I and S. Shinkai, Top. Curr. Chem., 2005, 258, 119. 12 L. A. Estroff and A. D. Hamilton, Chem. Rev., 2004, 104, 1201. 13 N. M. Sangeetha and U. Maitra, Chem. Soc. Rev., 2005, 34, 821. 14 R. Hirst, B. Escuder, J. F. Miravet and D. K. Smith, Angew. Chem., Int. Ed., 2008, 47, 8002. 15 P. Dastidar, Chem. Soc. Rev., 2008, 37, 2699. 16 M.-O. M. Piepenbrock, G. O. Lloyd, N. Clarke and J. W. Steed, Chem. Rev., 2010, 110, 1960. 17 (a) A. Kishimura, T. Yamashita and T. Aida, J. Am. Chem. Soc., 2005, 127, 179; (b) P. C. Andrews, P. C. Junk, M. Massi and M. Silberstein, Chem. Commun., 2006, 3317. 18 S. Kawano, N. Fujita and S. Shinkai, J. Am. Chem. Soc., 2004, 126, 8592. 19 K. Tsuchiya, Y. Orihara, Y. Kondo, N. Yoshino, T. Ohkubo, H. Abe and M. J. Sakai, J. Am. Chem. Soc., 2004, 126, 12282. 20 T. Tu, W. Assenmacher, H. Peterlik, R. Weisbarth, M. Nieger and tz, Angew. Chem., Int. Ed., 2007, 46, 6368. K. H. Do 21 B. Xing, M.-F. Chio and B. Xu, Chem.Eur. J., 2002, 8, 5028. 22 K. Kuroiwa, T. hibata, A. Takada, N. Nemoto and N. Kimizuka, J. Am. Chem. Soc., 2004, 126, 2016. 23 O. Roubeau, A. Colin, V. Schmitt and R. Clerac, Angew. Chem., Int. Ed., 2004, 43, 3283. 24 M. Shirakawa, N. Fujita, T. Tani, K. Kaneko, M. Ojima, A. Fujii, M. Ozaki and S. Shinkai, Chem.Eur. J., 2007, 13, 4155. 25 W. Weng, J. B. Beck, A. M. Jamieson and S. J. Rowan, J. Am. Chem. Soc., 2006, 128, 11663. 26 (a) H.-J. Kim, J.-H. Lee and M. Lee, Angew. Chem., Int. Ed., 2005, 44, 5810; (b) M.-O. Piepenbrock, N. Clarke and J. W. Steed, Langmuir, 2009, 25, 8451. 27 (a) J. Tao, Z.-J. Ma, R.-B. Huang and L.-S. Zheng, Inorg. Chem., 2004, 43, 6133; (b) W. Lee and J. J. Vittal, Chem. Rev., 2011, 111, 688. 28 J. H. Lee, H. Lee, S. Seo, M. L. Seo, S. Kang, J. Y. Lee and J. H. Jung, New J. Chem., 2011, 35, 1054. 29 J. H. Lee, S. Kang, J. Jaworski, K.-Y. Kwon, M. L. Seo, J. Y. Lee and J. H. Jung, Chem.Eur. J., 2012, 18, 765. 30 H. Lee, J. H. Lee, S. Kang, J. Y. Lee, G. John and J. H. Jung, Chem. Commun., 2011, 47, 2937. 31 F. Meench, M. Rauber, C. Stegmann, S. Lauterbach, U. Kunz, H.-J. Kleebe and W. Ensinger, Nanotechnology, 2011, 22, 415602. 32 F. M. Kelly and J. H. Johnston, ACS Appl. Mater. Interfaces, 2011, 3, 1083. 33 H. Basit, A. Pal, S. Sen and S. Bhattacharya, Chem.Eur. J., 2008, 14, 6534. 34 S. Dutta, A. Shome, S. Debnath and P. K. Das, Soft Matter, 2009, 5, 1607. 35 X. J. Fu, N. X. Wang, S. Z. Mang, H. Wang and Y. J. Yang, J. Inorg. Mater., 2008, 23, 393. 36 C. S. Love, V. Chechik, D. K. Smith, K. Wilson, I. Ashworth and C. Brennan, Chem. Commun., 2005, 1971. 37 R. N. Mitra and P. K. Das, J. Phys. Chem. C, 2008, 112, 8159. 38 E. D. Sone, E. R. Zubarev and S. I. Stupp, Small, 2005, 1, 694. 39 P. K. Vemula and G. John, Chem. Commun., 2006, 2218. 40 S. Porel, S. Singh, S. S. Harsha, D. N. Rao and T. P. Radhakrishnan, Chem. Mater., 2005, 17, 9.

Conclusions
We have investigated the gelling properties of tetrazole-based ligands with AgClO4. The gel formation of ligand 1 is dependent on the concentration of AgClO4. The strength of the gel is likely to arise from the retardation of the photodecomposition of Ag(I) within the gel, possibly by coordination of the tetrazole, pyridine moieties, and amide group with the growing nanoparticle. The size of the nanoparticle can be inuenced by controlling the concentration of AgClO4 during gel formation. In addition, metallogel 1 with AgClO4 produced a small and narrow distribution of silver nanoparticles. The samples exhibit complex rheological behavior depending on the initial concentration of AgClO4 and the presence of nanoparticles. The silver nanoparticles deposited onto the gel bers showed high catalytic activity in the reduction reaction of the nitro compound 4-NP. This is the rst example for the catalytic ability of silver nanoparticles deposited onto the gel bers. The present results emphasize the validity of ligand design that includes anion- and metal-binding in realizing metallogel systems with versatile and stimuli-responsive properties. These concepts should open the door for a wide range of responsive soft materials.

Acknowledgements
This work was supported by a grant from the World Class University (WCU) Program (R32-2008-000-20003-0) and NRF (2012-0003698) supported from the Ministry of Education, Science, S. Korea. In addition, this work was partially supported by a grant from the Next-Generation BioGreen 21 Program (SSAC, grant#: PJ008109), Rural development Administration, S. Korea.
6562 | Soft Matter, 2012, 8, 65576563

This journal is The Royal Society of Chemistry 2012

View Article Online

41 W. Wenseleers, F. Stellacci, T. Meyer-Friedrichsen, T. Mangel, C. A. Bauer, S. J. K. Pond, S. R. Marder and J. W. Perry, J. Phys. Chem. B, 2002, 106, 6853. 42 S. Pal, Y. K. Tak and J. M. Song, Appl. Environ. Microbiol., 2007, 73, 1712. 43 L. L. Zhao, K. L. Kelly and G. C. Schatz, J. Phys. Chem. B, 2003, 107, 7343. 44 Y. Lu, G. L. Liu and L. P. Lee, Nano Lett., 2005, 5, 5. 45 J. C. Hulteen, D. A. Treichel, M. T. Smith, M. L. Duval, T. R. Jensen and R. P. Van Duyne, J. Phys. Chem. B, 1999, 103, 3854. 46 P. Mukherjee, A. Ahmad, D. Mandal, S. Senapati, S. R. Sainkar, M. I. Khan, R. Parishcha, P. V. Ajaykumar, M. Alam, R. Kumar and M. Sastry, Nano Lett., 2001, 1, 515. 47 M. O. M. Piepenbrock, N. Clarke and J. W. Steed, Soft Matter, 2011, 7, 2412. 48 (a) M. Dinc a, A. F. Yu and J. R. Long, J. Am. Chem. Soc., 2006, 128, 8904; (b) M. Dinc a, A. F. Yu, Y. Liu, C. M. Brown, D. A. Neumann and J. R. Long, J. Am. Chem. Soc., 2006, 128, 16876. 49 M. J. Frisch, Gaussian 03, revision B05, Gaussian Inc, Pittsburg, PA 2003.

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.

This journal is The Royal Society of Chemistry 2012

Soft Matter, 2012, 8, 65576563 | 6563

Addition and correction

View Article Online

Note from RSC Publishing This article was originally published with incorrect page numbers. This is the corrected, final version. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

Published on 21 May 2012. Downloaded by Rani Durgavati Vishwavidyalaya on 28/10/2013 08:23:22.