Au137(SR)56 nanomolecules: composition, optical spectroscopy, electrochemistry and electrocatalytic reduction of CO2.

Au137(SR)56, a nanomolecule with a precise number of metal atoms and ligands, was synthesized. The composition was confirmed by MALDI and ESI mass spectrometry using three unique ligands (-SCH2CH2Ph, -SC6H13, and -SC4H9) and nano-alloys with Ag and Pd. The electrocatalytic properties were tested for CO2 reduction.

Au(144-x)Cu(x)(SC6H13)60 nanomolecules: effect of Cu incorporation on composition and plasmon-like peak emergence in optical spectra.

Au144-xCux(SR)60 alloy nanomolecules were synthesized and characterized by using ESI-MS to atomic precision. A maximum of 23 copper atoms replace the gold atoms. When the number of copper atoms is higher than eight, a surface plasmon-like peak appears at ∼520 nm. Based on the fundamental elemental properties of Au and Cu, we predict a mixed atomic ordering and incorporation of Cu atoms into the Au12 and Au42 shells of the proposed icosahedral structure model of the 144-atom nanomolecule.

Ligand exchange reactions on Au(38) and Au(40) clusters: a combined circular dichroism and mass spectrometry study.

The thiolate-for-thiolate ligand exchange reaction between the stable Au(38)(2-PET)(24) and Au(40)(2-PET)(24) (2-PET: 2-phenylethanethiol) clusters and enantiopure BINAS (BINAS: 1,1'-binaphthyl-2,2'-dithiol) was investigated by circular dichroism (CD) spectroscopy in the UV/vis and MALDI mass spectrometry (MS). The ligand exchange reaction is incomplete, although a strong optical activity is induced to the resulting clusters. The clusters are found to be relatively stable, in contrast to similar reactions on [Au(25)(2-PET)(18)](-) clusters. Maximum anisotropy factors of 6.6 × 10(-4) are found after 150 h of reaction time. During the reaction, a varying ratio between Au(38) and Au(40) clusters is found, which significantly differs from the starting material. As compared to Au(38), Au(40) is more favorable to incorporate BINAS into its ligand shell. After 150 h of reaction time, an average of 1.5 and 4.5 BINAS ligands is found for Au(38) and Au(40) clusters, respectively. This corresponds to exchange of 3 and 9 monodentate 2-PET ligands. To show that the limited exchange with BINAS is due to the bidentate nature of the ligand, exchange with thiophenol was performed. The monodentate thiophenol exchange was found to be faster, and more ligands were exchanged when compared to BINAS.

Ion mobility mass spectrometry of Au25(SCH2CH2Ph)18 nanoclusters.

Ion mobility mass spectrometry (IM-MS) can separate ions based on their size, shape, and charge as well as mass-to-charge ratios. Here, we report experimental IM-MS and IM-MS/MS data of the Au(25)(SCH(2)CH(2)Ph)(18)(-) nanocluster. The IM-MS of Au(25)(SCH(2)CH(2)Ph)(18)(-) exhibits a narrow, symmetric drift time distribution that indicates the presence of only one structure. The IM-MS/MS readily distinguishes between the fragmentation of the outer protecting layer, made from six [-SR-Au-SR-Au-SR-] "staples' where R = CH(2)CH(2)Ph, and the Au(13) core. The fragmentation of the staples is characterized by the predominant loss of Au(4)(SR)(4) from the cluster and the formation of eight distinct bands. The consecutive eight bands contain an increasing variety of Au(l)S(m)R(n)(-) product ions due to the incremental fragmentation of the outer layer of Au(21)X(14)(-), where X = S or SCH(2)CH(2)Ph. The mobility of species in each individual band shows that the lower mass species exhibit greater collision cross sections, facilitating the identification of the Au(l)S(m)R(n)(-) products. Below the bands, in the region 1200-2800 m/z, product ions relating to the fragmentation of the Au(13) core can be observed. In the low mass 50-1200 m/z region, fragment ions such as Au(SR)(2)(-), Au(2)(SR)(3)(-), Au(3)(SR)(4)(-), and Au(4)(SR)(5)(-) are also observed, corresponding to the large fragments Au(25-x)(SR)(18-(x+1)). The study shows that most of the dominant large fragments are of the general type Au(21)X(14)(-/+), and Au(17)X(10)(-/+) with electron counts of 8 and 6 in negative and positive mode, respectively. This suggests that geometric factors may outweigh electronic factors in the selection of Au(25)(SR)(18) structure.

Nanocluster size evolution studied by mass spectrometry in room temperature Au25(SR)18 synthesis.

We show that MALDI mass spectrometry, suitable for mixtures, is an indispensable tool in probing the mechanism of nanocluster synthesis enabling positive identification of nanoclusters. The size evolution of the mixture of larger clusters (Au(102), Au(68), Au(38)) to form highly monodisperse Au(25) nanoclusters is demonstrated and probably includes the participation of Au(I) thiolate. The size evolution via structural reconstruction of the larger cores such as 38, approximately 44, 68, and 102 to a Au(25) nanocluster has been discussed.