In this work we studied different properties of gold and silver nanoclusters (AuNCs and AgNCs) protected by the chiral ligands L-glutathione (L-GSH), and N-acetyl-L-cysteine (NALC), and we present a thorough characterization of the synthesized clusters. The synthesis was performed by reduction of the corresponding metal salt with NaBH 4 . Fractions of gold nanoclusters with different sizes were isolated by methanol-induced precipitation. The ellipticity of the clusters was obtained by circular dichroism (CD) spectroscopy, showing that the chirality of the ligands is transferred to the metal core either in its structure or at least in its electronic states via perturbation of the electronic field of the ligands. The optical properties of gold and silver nanoclusters in water were studied by UV−vis spectroscopy. The absorption signal of the clusters shows characteristic bands, which can be assigned to plasmonic transitions of the metal core. In addition, UV−vis spectroscopy has served as a tool for studying the stability of these clusters in air. In general, gold nanoclusters are highly stable in air, and it was found that the stability of Au n (NALC) m clusters even exceeds that of Au n (SG) m clusters. In contrast to gold clusters, silver nanoclusters very often tend to decompose upon exposure to air. We found, however, that Ag n (NALC) m are surprisingly stable at atmospheric pressures. The average molecular formula of the nanoclusters was determined by thermogravimetric analysis (TGA). The particle sizes of AuNCs and AgNCs were assessed by transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) analysis. For studying the fluorescent properties of the metal nanoparticles, photoluminescence spectroscopy (PL) was performed. In summary, we succeeded to synthesize ligand-protected silver clusters (Ag n (NALC) m ) with very high stability and rather narrow size distribution; furthermore, we could show the controlled precipitation to be applicable to other systems, such as that Au n (NALC) m , yielding two fraction of very narrow size distribution.

Silver nanoclusters protected by 2-phenylethanethiol (1), 4-fluorothiophenol (2), and l-glutathione (3) ligands were successfully synthesized. The optical properties of the prepared silver nanoclusters were studied. The absorption signal of Ag@SCH2CH2Ph in toluene can be found at 469 nm, and Ag@SPhF in THF shows two absorption bands at 395 and 462 nm. Ag@SG in water absorbs at 478 nm. Mie theory in combination with the Drude model clearly indicates the peaks in the spectra originate from plasmonic transitions. In addition, the damping constant as well as the dielectric constant of the surrounding medium was determined. In addition, the CD spectra of silver nanoclusters protected by the three ligands (1–3) were also studied. As expected, only the clusters of type 3 gave rise to chiroptical activity across the visible and near-ultraviolet regions. The location and strength of the optical activity suggest an electronic structure of the metal that is highly sensitive to the chiral environment imposed by the glutathione ligand. The morphology and size of the prepared nanoclusters were analyzed by using transmission electron microscopy (TEM). TEM analysis showed that the particles of all three types of silver clusters were small than 5 nm, with an average size of around 2 nm. The analysis of the FTIR spectra elucidated the structural properties of the ligands binding to the nanoclusters. By comparing the IR absorption spectra of pure ligands with those of the protected silver nanoclusters, the disappearance of the S–H vibrational band (2535–2564 cm–1) in the protected silver nanoclusters confirmed the anchoring of ligands to the cluster surface through the sulfur atom. By elemental analysis and thermogravimetric analysis, the Ag/S ratio and, hence, the number of ligands surrounding a Ag atom could be determined

Through the discovery of ligand protected metal clusters with cores of a precise number of atoms, the exploration of the third dimension of the periodic table for fundamental research and also for applications has become less remote. So far, the exact number of metal atoms in the core has been determined unambiguously only using mass spectrometry and single crystal X-ray diffraction. Gold clusters protected by 2-phenylethanethiol ligands, for instance, show distinct magic numbers that correspond to either electronic or geometric shell closings. For efficient control of their synthesis simple-to-use in situ spectroscopies are required. In the specific case of Au25(SCH2CH2Ph)18 clusters (1) we found a distinct shift of the aromatic C-H stretching band from 3030-3100 cm(-1) to below 3000 cm(-1) whose origin is discussed as an electronic interaction of the aromatic rings of the ligands with each other or with the gold core. This IR-feature is specific for Au25; the spectra of Au38(SCH2CH2Ph)24 (2) and Au144(SCH2CH2Ph)60 (3) clusters do not show this distinct shift and their IR-spectra in the C-H stretching regime are similar to that of the bare ligand. This significant change in the IR spectrum of Au25(SCH2CH2Ph)18 is not only of fundamental interest but also allows for in situ determination of the purity and monodispersity of the sample using FTIR spectroscopy during synthesis.

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