Abstract
We report the controlled growth of Au25(SR)18 and Au38(SR)24 (where R = CH2CH2Ph) nanoclusters of molecular purity via size-focusing from the same crude product that contains a distribution of nanoclusters. In this method, gold salt was first mixed with tetraoctylammonium bromide (TOAB), and then reacted with excess thiol to form Au(I)-SR polymers in THF (as opposed to toluene in previous work), followed by NaBH4 reduction. The resultant crude product contains polydisperse nanoclusters and was then used as the common starting material for controlled growth of Au25(SR)18 and Au38(SR)24, respectively. In Route I, Au25(SR)18 nanoclusters of molecular purify were produced from the crude product after 6 h aging at room temperature. In Route II, the crude product was isolated and further subjected to thermal thiol etching in a toluene solution containing excess thiol, and one obtained pure Au38(SR)24 nanoclusters, instead of Au25(SR)18. This work not only provides a robust and simple method to prepare both Au25(SR)18 and Au38(SR)24 nanoclusters, but also reveals that these two nanoclusters require different environments for the size-focusing growth process.
Similar content being viewed by others
References
Jin R, Zhu Y, Qian H. Quantum-sized gold nanoclusters: Bridging the gap between organometallics and nanocrystals. Chem Eur J, 2011, 17(24): 6584–6593
Whetten RL, Price RC. Nano-golden order. Science, 2007, 318(5849): 407–408
Jiang D, Whetten RL. Magnetic doping of a thiolated-gold superatom: First-principles density functional theory calculations. Phys Rev B, 2009, 80: 115402–115405
Pei Y, Gao Y, Zeng XC. Structural prediction of thiolate-protected Au38: A face-fused bi-icosahedral Au core. J Am Chem Soc, 2008, 130: 7830–7832
Lopez-Acevedo O, Akola J, Whetten RL, Gronbeck H, Hakkinen H. Structure and bonding in the ubiquitous icosahedral metallic gold cluster Au144(SR)60. J Phys Chem C, 2009, 113(13): 5035–5038
Zhu M, Aikens CM, Hollander FJ, Schatz GC, Jin R. Correlating the crystal structure of a thiol-protected Au25 cluster and optical properties. J Am Chem Soc, 2008, 130(18): 5883–5885
Jin R, Qian H, Zhu Y, Das A. Atomically precise nanoparticles: A new frontier in nanoscience. J Nanosci Lett, 2011, 1(2): 72–78
Wyrwas RB, Alvarez MM, Khoury JT, Price RC, Schaaff TG, Whetten RL. The colours of nanometric gold: Optical response functions of selected gold-cluster thiolates. Eur Phys J D, 2007, 43: 91–95
Parker JF, Weaver JEF, McCallum F, Fields-Zinna CA, Murray RW. Synthesis of monodisperse [Oct4N+][Au25(SR)18] nanoparticles with some mechanistic observations. Langmuir, 2010, 26(16): 13650–13654
Negishi Y, Chaki NK, Shichibu Y, Whetten RL, Tsukuda T. Origin of magic stability of thiolated gold clusters: A case study on Au25(SC6H13)18. J Am Chem Soc, 2007, 129(37): 11322–11323
Dharmaratne AC, Krick T, Dass A. Nanocluster size evolution studied by mass spectrometry in room temperature Au25(SR)18 synthesis. J Am Chem Soc, 2009, 131(38): 13604–13605
Negishi Y, Kurashige W, Niihori Y, Iwasa T, Nobusada K. Isolation structure and stability of a dodecanethiolate-protected Pd1Au24 cluster. Phys Chem Chem Phys, 2010, 12: 6219–6225
Gautier C, Burgi T. Chiral gold nanoparticles. ChemPhysChem, 2009, 10: 483–492
Habeeb Muhammed MA, Pradeep T. Au25@SiO2: Quantum clusters of gold embedded in silica. Small, 2011, 7: 204–208
Devadas MS, Kim J, Sinn E, Lee D, Goodson III T, Ramakrishna G. Unique ultrafast visible luminescence in monolayer-protected Au25 clusters. J Phys Chem C, 2010, 114(51): 22417–22423
Qian H, Sfeir MY, Jin R. Ultrafast relaxation dynamics of [Au25(SR)18]q nanoclusters: Effects of charge state. J Phys Chem C, 2010, 114: 19935–19940
Tsukuda T, Tsunoyama H, Sakurai H. Aerobic oxidations catalyzed by colloidal nanogold. Chem Asian J, 2011, 6(3): 736–748
Zhu Y, Qian H, Jin R. Catalysis opportunities of atomically precise gold nanoclusters. J Mater Chem, 2011. 21: 6793–6799
Zhu M, Lanni E, Garg N, Bier ME, Jin R. Kinetically controlled high-yield synthesis of Au25 clusters. J Am Chem Soc, 2008, 130(4): 1138–1139
Wu Z, Suhan J, Jin R. One-pot synthesis of atomically monodisperse thiol-functionalized Au25 nanoclusters. J Mater Chem, 2009, 19(5): 622–626
Zhu M, Aikens CM, Hollander FJ, Schatz GC, Jin R. Correlating the crystal structure of a thiol-protected Au25 Cluster and optical properties. J Am Chem Soc, 2008, 130: 5883–5885
Zhu M, Qian H, Jin R. Thiolate-protected Au20 clusters with a large energy gap of 2.1 eV. J Am Chem Soc, 2009, 131(21): 7220–7221
Zhu M, Qian H, Jin R. Thiolate-protected Au24(SC2H4Ph)20 nanoclusters: Superatoms or not? J Phys Chem Lett, 2010, 1(6): 1003–1007
Nimmala PR, Dass A. Au36(SPh)23 nanomolecules. J Am Chem Soc, 2011, 133: 9175–9177
Chaki NK, Negishi Y, Tsunoyama H, Shichibu Y, Tsukuda T. Ubiquitous 8 and 29 kDa gold:alkanethiolate cluster compounds: Mass-spectrometric determination of molecular formulas and structural implications. J Am Chem Soc, 2008, 130(27): 8608–8610
Qian H, Zhu M, Andersen UN, Jin R. Facile large-scale synthesis of dodecanethiol-stabilized Au38 clusters. J Phys Chem A, 2009, 113(16): 4281–4284
Qian H, Zhu Y, Jin R. Size-focusing synthesis optical and electrochemical properties of monodisperse Au38(SC2H4Ph)24 nanoclusters. ACS Nano, 2009, 3(11): 3795–3803
Qian H, Zhu Y, Jin R. Isolation of ubiquitous Au40(SR)24 clusters from the 8 kDa gold clusters. J Am Chem Soc, 2010, 132: 4583–4585
Tsunoyama R, Tsunoyama H, Pannopard P, Limtrakul J, Tsukuda T. MALDI mass analysis of 11 kDa gold clusters protected by octadecanethiolate ligands. J Phys Chem C, 2010, 114(38): 16004–16009
Qian H, Jin R. Synthesis and electrospray mass spectrometry determination of thiolate-protected Au55(SR)31 nanoclusters. Chem Commun, 2011, (41): 11462–11464
Hulkko E, Lopez-Acevedo O, Koivisto J, Levi-Kalisman Y, Kornberg RD, Pettersson M, Häkkinen H. Electronic and vibrational signatures of the Au102(p-MBA)44 cluster. J Am Chem Soc, 2011, 133: 3752–3755
Qian H, Jin R. Controlling nanoparticles with atomic precision: The case of Au144(SCH2CH2Ph)60. Nano Lett, 2009, 9(12): 4083–4087
Qian H, Jin R. Ambient synthesis of Au144(SR)60 nanoclusters in methanol. Chem Mater, 2011, 23(8): 2209–2217
Qian H, Zhu Y, Jin R. Atomically precise gold nanocrystal molecules with surface plasmon resonance. Proc Natl Acad Sci USA, 2012, 109(3): 696–700
Jin R, Qian H, Wu Z, Zhu Y, Zhu M, Mohanty A, Garg N. Size focusing: A methodology for synthesizing atomically precise gold nanoclusters. J Phys Chem Lett, 2010, 1: 2903–2910
Wu Z, MacDonald M, Chen J, Zhang P, Jin R. Kinetic control and thermodynamic selection in the synthesis of atomically precise gold nanoclusters. J Am Chem Soc, 2011, 133: 9670–9673
Qian H, Eckenhoff WT, Zhu Y, Pintauer T, Jin R. Total structure determination of thiolate-protected Au38 nanoparticles. J Am Chem Soc, 2010, 132(24): 8280–8281
Qian H, Zhu M, Gayathri C, Gil RR, Jin R. Chirality of gold nanoclusters probed by NMR spectroscopy. ACS Nano, 2011, 5: 8935–8942
Zhu M, Eckenhoff WT, Pintauer T, Jin R. Conversion of anionic [Au25(SCH2CH2Ph)18]− cluster to charge neutral cluster via air oxidation. J Phys Chem C, 2008, 112: 14221–14224
Parker JF, Choi JP, Wang W, Murray RW. Electron self-exchange dynamics of the nanoparticle couple [Au25(SC2Ph)18]0/1 by nuclear magnetic resonance line-broadening. J Phys Chem C, 2008, 112: 13976–13981
Zhu M, Chan G, Qian H, Jin R. Unexpected reactivity of Au25(SCH2CH2Ph)18 nanoclusters with salts. Nanoscale, 2011, 3: 1703–1707
Venzo A, Antonello S, Gascon JA, Guryanov I, Leapman RD, Perera NV, Sousa AA, Zamuner M, Zanella A, Maran F. Effect of the charge state (z = −1 0 +1) on the nuclear magnetic resonance of monodisperse Au25[S(CH2)2Ph]18 z clusters. Anal Chem, 2011, 83(16): 6355–6362
Liu Z, Zhu M-Z, Meng X, Xu G, Jin R. Electron t7ransfer between [Au25(SC2H4Ph)18]−TOA+ and Oxoammonium Cations J Phys Chem Lett, 2011 2: 2104–2109
Zhu M, Aikens CM, Hendrich MP, Gupta R, Qian H, Schatz GC, Jin R. Reversible switching of magnetism in thiolate-protected Au25 superatoms. J Am Chem Soc, 2009, 131(7): 2490–2492
Yao H, Fukui T, Kimura K. Asymmetric transformation of monolayer-protected gold nanoclusters via chiral phase transfer. J Phys Chem C, 2008, 112: 16281–16285
Knoppe S, Dharmaratne AC, Schreiner E, Dass A, Burgi T. Ligand exchange reactions on Au38 and Au40 clusters: A combined circular dichroism and mass spectrometry study. J Am Chem Soc, 2010, 132(47): 16783–16789
Zhu M, Qian H, Meng X, Jin S, Wu Z, Jin R. Chiral Au25 nanospheres and nanorods: Synthesis and insight into the origin of chirality. Nano Lett, 2011, 11(9): 3963–3969
George A, Shibu ES, Maliyekkal SM, Bootharaju MS, Pradeep T. Luminescent freestanding composite films of Au15 for specific metal ion sensing. ACS Appl Mater Interf, 2012, 4(2): 639–644
Wu Z, Jin R. On the ligand’s role in the fluorescence of gold nanoclusters. Nano Lett, 2010, 10(7): 2568–2573
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Qian, H., Liu, C. & Jin, R. Controlled growth of molecularly pure Au25(SR)18 and Au38(SR)24 nanoclusters from the same polydispersed crude product. Sci. China Chem. 55, 2359–2365 (2012). https://doi.org/10.1007/s11426-012-4669-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-012-4669-8