6762
J. Athilakshmi, D. K. Chand / Tetrahedron Letters 51 (2010) 6760–6762
0.30
0.25
0.20
0.15
0.10
0.05
0.00
Acknowledgments
D.K.C. thanks CSIR for a possible financial support. J.A. thanks IIT
Madras for a fellowship.
Supplementary data
Supplementary data (synthesis of ligands, details of materials
characterization and property evaluation by UV–vis, powder XRD,
TEM, HRTEM, EDAX, CV and NMR methods and other graphs) asso-
ciated with this article can be found, in the online version, at
2+
Hg blank
+
2+
+
2+
2+
Mg
+
Ag Pb
metal acetate
Na Zn
NH
4
References and notes
1. (a) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. Rev. 2000, 100, 2537; (b)
Martnez-Mez, R.; Sancenn, F. Chem. Rev. 2003, 103, 4419; (c) Schmidtchen, F. P.;
Berger, M. Chem. Rev. 1997, 97, 1609.
Figure 4. A comparison showing optical density (at 417 nm) of various solution
obtained from the combination of 4 mL of 2 mM of methanolic L1 with 0.1 mL of
1 mM of aqueous metal acetates after standing for 30 min.
2. Silver, S. FEMS Microbiol. Rev. 2003, 27, 341.
3. (a) Wang, L.; Liang, A.-N.; Chen, H.-Q.; Liu, Y.; Qian, B.-B.; Fu, J. Anal. Chim. Acta.
2008, 616, 170; (b) Cox, M. T.; Hill, L. M. R.; Gahan, L. R. Analyst 1999, 124, 859;
(c) Wang, J.-H.; Wang, H.-Q.; Zhang, H.-L.; Li, X.-Q.; Hua, X.-F.; Cao, Y.-C.;
Huang, Z.-L.; Zhao, Y.-D. Anal. Bioanal. Chem. 2007, 388, 969; (d) Kagan, D.;
Calvo-Marzal, P.; Balasubramanian, S.; Sattayasamitsathit, S.; Manesh, K. M.;
Flechsig, G.-U.; Wang, J. J. Am. Chem. Soc. 2009, 131, 12082; (e) Wygladacz, K.;
Radu, A.; Xu, C.; Qin, Y.; Bakker, E. Anal. Chem. 2005, 77, 4706.
4. (a) Iyoshi, S.; Taki, M.; Yamamoto, Y. Inorg. Chem. 2008, 47, 3946; (b) Chatterjee,
A.; Santra, M.; Won, N.; Kim, S.; Kim, J. K.; Kim, S. B.; Ahn, K. H. J. Am. Chem. Soc.
2009, 131, 2040.
5. (a) Al-Kady, A. S.; Gaber, M.; Hussein, M. M.; Ebeid, E.-Z. M. J. Phys. Chem. A
2009, 113, 9474.
6. (a) Kumar, M.; Mahajan, R. K.; Sharma, V.; Singh, H.; Sharma, N.; Kaur, I.
Tetrahedron Lett. 2001, 42, 5315; (b) Kimura, K.; Yajima, S.; Tatsumi, K.;
Yokoyama, M.; Oue, M. Anal. Chem. 2000, 72, 5290.
7. (a) Schmittel, M.; Lin, H. Inorg. Chem. 2007, 46, 9139; (b) Casabb, J.; Flor, T.; Hill,
M. N. S.; Jenkins, H. A.; Lockhart, J. C.; Loeb, S. J.; Romero, I.; Teixidor, F. Inorg.
Chem. 1995, 34, 5410; (c) Amendola, V.; Esteban-Gómez, D.; Fabbrizzi, L.;
Licchelli, M.; Monzani, E.; Sancenón, F. Inorg. Chem. 2005, 44, 8690.
8. (a) Jain, P. K.; Huang, X.; El-Sayed, I. H.; El-Sayed, M. A. Acc. Chem. Res. 2008, 41,
1578; (b) Xie, F.; Baker, M. S.; Goldys, E. M. J. Phys. Chem. B 2006, 110, 23085.
9. (a) Creighton, J. A.; Eadon, D. G. J. Chem. Soc., Faraday Trans. 1991, 87, 3881; (b)
Doty, R. C.; Tshikhudo, T. R.; Brust, M.; Fernig, D. G. Chem. Mater. 2005, 17,
4630; (c) Wiley, B. J.; Im, S. H.; Li, Z.-Y.; Mclellan, J.; Siekkinen, A.; Xia, Y. J. Phys.
Chem. B 2006, 110, 15666.
10. (a) Grubbs, R. B. Nat. Mater. 2007, 6, 553; (b) Ledwith, D. M.; Whelan, A. M.;
Kelly, J. M. J. Mat. Chem. 2007, 17, 2459.
11. (a) Wiley, B.; Sun, Y.; Xia, Y. Acc. Chem. Res. 2007, 40, 1067; (b) Dong, X.; Ji, X.;
Wu, H.; Zhao, L.; Li, J.; Yang, W. J. Phys. Chem. C 2009, 113, 6573; (c) Canamares,
M. V.; Garcia-Ramos, J. V.; Gomez-Varga, J. D.; Domingo, C.; Sanchez-Cortes, S.
Langmuir 2005, 21, 8546.
12. (a) Yamamoto, M.; Nakamoto, M. J. Mater. Chem. 2003, 13, 2064; (b) Ramajo, L.;
Parra, R.; Reboredo, M.; Castro, M. J. Chem. Sci. 2009, 121, 83; (c) Ujihara, M.;
Orbulescu, J.; Imae, T.; Leblanc, R. M. Langmuir 2005, 21, 6846; (d) Chen, M.;
Feng, Y.-G.; Wang, X.; Li, T.-C.; Zhang, J.-Y.; Qian, D.-J. Langmuir 2007, 23, 5296;
(e) Zhang, Y.; Peng, H.; Huang, W.; Zhou, Y.; Zhang, X.; Yan, D. J. Phys. Chem. C
2008, 112, 2330; (f) Aymonier, C.; Schlotterbeck, U.; Antonietti, L.; Zacharias,
P.; Thomann, R.; Tiller, J. C.; Mecking, S. Chem. Commun. 2002, 3018; (g)
Kalidindi, S. B.; Sanyal, U.; Jagirdar, B. R. Inorg. Chem. 2010, 49, 3965.
13. Chen, D.; Martell, A. E. Tetrahedron 1991, 47, 6895.
14. (a) Li, T.; Lin, H.; Li, T.; He, W.; Li, Z.; Zhang, Y.; Zhu, Y.; Guo, Z. Inorg. Chim. Acta
2009, 362, 967; (b) Graham, B.; Spiccia, L.; Batten, S. R.; Skelton, B. W.; White,
A. H. Inorg. Chim. Acta 2005, 358, 3983; (c) Gao, J.; Reibenspies, J. H.; Martell, A.
E. Inorg. Chim. Acta 2002, 335, 125; (d) He, W.; Liu, F.; Duan, C.; Guo, Z.; Zhou,
S.; Liu, Y.; Zhu, L. Inorg. Chem. 2001, 40, 7065.
in the final solutions. It is shown clearly that Ag+ ion can be visually
sensed at low concentrations (Fig. S8, Supplementary data). A linear
correlation exists between the absorbance at 420 nm as increase in
the concentration of Ag+ ions over the range of 10ꢀ5–10ꢀ4 M concen-
tration with the relative coefficient of 0.996 is exhibited. (Fig. S9,
Supplementary data). The formation Ag nanoparticles was con-
firmed by the appearance of the surface plasmon peak in TEM image
and UV–vis spectra (Figs. S10 and S11, Supplementary data).
The formation of AgNPs from other silver salts having a range of
counter anions was performed at lower concentration of the silver
ion (ꢁ24
lM). Silver salts such as AgBF4, AgPF6, AgCF3SO3, AgNO3,
AgCl, and AgOAc were taken for this study. All the solutions be-
haved similarly and showed the formation of AgNPs which was
monitored by UV–vis spectroscopy (Figs. S11 and S12, Supplemen-
tary data). This suggests that, anions have little/no interference in
detection of silver ion under the condition employed.
When the experiments were performed using other metal ace-
tates, such as NH4þ, Hg2+, Mg2+, Na+, Pb2+, and Zn2+ and other metal
chlorides, such as Ba2+, Ca2+, Cd2+, Co2+, Cu2+, Fe3+, Hg2+, K+, Li+, Mg2+
,
Na+, Ni2+, Pb2+, and Zn2+, the solution remained colorless. The absor-
bance of a variety of metal acetates at 417 nm is shown (Fig. 4),
which implies the selectivity of silver ions over other metal cations.
We tested the selectivity of silver ions in the presence of ten
fold excess of other metal ions such as Na+, Ca2+, K+, Mg2+, Na+,
Pb2+, and Zn2+. To the methanolic solution of L1 (4 mL of 2 mM)
was added 0.1 mL of aqueous solution of 1 mM of AgOAc and also
0.2 mL of aqueous solution of 5 mM of other metal acetates. As
shown in (Fig. S13, Supplementary data) the presence of other me-
tal ions did not lower the absorbance rather, result in the slight in-
crease in absorbance in the presence of other metal ions. This is
possibly due to the growth of the AgNPs size due to the presence
of additional metal salts which can act as seed.18
In conclusion, we have reported a room temperature synthesis
of AgNPs demonstrating the special role of a hexazamacrocycle li-
gand in aqueous-methanol. The ligand helps in reduction and sub-
15. He, W.; Ye, Z.; Xu, Y.; Guo, Z.; Zhu, L. Acta Crystallogr., Sect. C 2000, 56, 1019.
16. (a) Ragunathan, K. G.; Schneider, H.-J. Angew. Chem., Int. Ed. 1996, 35, 1219; (b)
Baldes, R.; Schneider, H.-J. Angew. Chem., Int. Ed. Engl. 1995, 34, 321; (c) Hortala,
M. A.; Fabbrizzi, L.; Marcotte, N.; Stomeo, F.; Taglietti, A. J. Am. Chem. Soc. 2003,
125, 20.
stantial stabilization probably through coordination and cation–
p
17. (a) Lee, J.-E.; Lee, J. Y.; Seo, J.; Lee, S. Y.; Kim, H. J.; Park, S.; Park, K.-M.; Lindoy, L.
F.; Lee, S. S. Polyhedron 2008, 27, 3004; (b) Ray, D.; Bharadwaj, P. K. Eur. J. Inorg.
Chem. 2006, 1771; (c) Tei, L.; Blake, A. J.; Cooke, P. A.; Caltagirone, C.; Demartin,
F.; Lippolis, V.; Morale, F.; Wilson, C.; Schröder, M. J. Chem. Soc., Dalton Trans.
2002, 1662; (d) Takemura, H.; Kon, N.; Tani, K.; Takehara, K.; Kimoto, J.;
Shinmyozu, T.; Inazu, T. J. Chem. Soc., Perkin Trans. 1997, 1, 239.
18. Tsuji, M.; Matsumoto, K.; Jiang, P.; Matsuo, R.; Tang, X.-L.; Sozana, K.;
Kamarudin, N. Colloids Surf., A 2008, 316, 266.
interaction attributed to the cyclic nature of the ligand. The ease
of generation of silver nanoparticles is utilized for the visual detec-
tion of the presence of silver ions at lower concentrations. Explora-
tion of such methodology can be useful for detecting other metal
cations by infusing the concepts of supramolecular chemistry
and nanochemistry.