Crystal structure determination has revolutionized modern science in biology, chemistry, and physics. However, the difficulty in obtaining periodic crystal lattices which are needed for X-ray crystal analysis has hindered the determination of atomic structure in nanomaterials, known as the "nanostructure problem". Here, by using rigid and bulky ligands, we have overcome this limitation and successfully solved the X-ray crystallographic structure of the largest reported thiolated gold nanomolecule, Au133S52. The total composition, Au133(SPh-tBu)52, was verified using high resolution electrospray ionization mass spectrometry (ESI-MS). The experimental and simulated optical spectra show an emergent surface plasmon resonance that is more pronounced than in the slightly larger Au144(SCH2CH2Ph)60. Theoretical analysis indicates that the presence of rigid and bulky ligands is the key to the successful crystal formation.

(Au-Ag)(144)(SR)(60) alloy nanomolecules were synthesized and characterized by ESI mass spectrometry to atomic precision. The number of Ag atoms can be varied by changing the incoming metal ratio and plateaus at ∼60. UV-vis data demonstrates that the electronic structure of the nanomolecules can be tuned by incorporation of silver atoms. Based on the proposed 3-shell structure of Au(144)(SR)(60), we hypothesize that the Ag atoms are selectively incorporated in to the symmetry equivalent 60-atom shell-having Au(12), Au(42), Ag(60) concentric shells with 30 -SR-Au-SR- protecting units.

The atomic arrangement of Au and Ag atoms in Au25-xAgx(SR)18 was determined by X-ray crystallography. Ag atoms were selectively incorporated in the 12 vertices of the icosahedral core. The central atom and the metal atoms in the six [-SR-Au-SR-Au-SR-] units were exclusively gold, with 100% Au occupancy. The composition of the crystals determined by X-ray crystallography was Au18.3Ag6.7(SCH2CH2Ph)18. This composition is in reasonable agreement with the composition Au18.8Ag6.2(SCH2CH2Ph)18 measured by electrospray mass spectrometry. The structure can be described in terms of shells as Au1@Au5.3Ag6.7@6×[-SR-Au-SR-Au-SR-]. Density functional theory calculations show that the electronic structure and optical absorption spectra are sensitive to the silver atom arrangement within the nanocluster.

The Raman spectra of a series of monolayer-protected gold clusters were investigated with special emphasis on the Au-S modes below 400 cm(-1). These clusters contain monomeric (SR-Au-SR) and dimeric (SR-Au-SR-Au-SR) gold-thiolate staples in their surface. In particular, the Raman spectra of Au-25(2-PET)(18)](0/-), Au-38(2-PET)(24), Au-40(2-PET)(24), and Au-144(2-PET)(60) (2-PET = 2-phenylethylthiol) were measured in order to study the influence of the cluster size and therefore the composition with respect to the monomeric and dimeric staples. Additionally, spectra of Au-25(2-PET)(18-2x) (S-/rac-BINAS)(x) (BINAS = 1,1'-binaphthy1-2,2'-dithiol), Au-25(CamS)(18) (CamS = 1R,4S-camphorthiol), and Au(n)BINAS(m) were measured to identify the influence of the thiolate ligand on the Au-S vibrations. The vibrational spectrum of Au-38(SCH3)(24) was calculated which allows the assignment of bands to vibrational modes of the different staple motifs. The spectra are sensitive to the size of the cluster and the nature of the ligand. Au-S-C bending around 200 cm(-1) shifts to slightly higher wavenumbers for the dimeric as compared to the monomeric staples. Radial Au-S modes (250-325 cm(-1)) seem to be sensitive toward the staple composition and the bulkiness of the ligand, having higher intensities for long staples and shifting to higher wavenumbers for sterically more demanding ligands. The introduction of only one BINAS dithiol has a dramatic influence on the Au-S vibrations because the molecule bridges two staples which changes their vibrational properties completely. Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 ...

Au(38-n)Ag(n)(SCH(2)CH(2)Ph)(24) alloy nanomolecules were synthesized, purified and characterized by MALDI TOF mass spectrometry. Similar to 25 and unlike 144 metal atom count AuAg alloy nanomolecules, incorporation of Ag atoms here results in loss or smearing out of distinct UV-vis features. We propose that the short and long staples contain Au atoms, while the inner core consists of both Au and Ag atoms.