title: Au133(SPh-tBu)52 nanomolecules: X-ray crystallography, optical, electrochemical, and theoretical analysis.
abstract: 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.
authors.affiliation: †Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677, United States.
authors.forename: Amala
authors.initials: A
authors.lastname: Dass
authors.affiliation: †Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677, United States.
authors.forename: Shevanuja
authors.initials: S
authors.lastname: Theivendran
authors.affiliation: †Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677, United States.
authors.forename: Praneeth Reddy
authors.initials: PR
authors.lastname: Nimmala
authors.affiliation: †Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677, United States.
authors.forename: Chanaka
authors.initials: C
authors.lastname: Kumara
authors.affiliation: †Department of Chemistry and Biochemistry, University of Mississippi, Oxford, Mississippi 38677, United States.
authors.forename: Vijay Reddy
authors.initials: VR
authors.lastname: Jupally
authors.forename: Alessandro
authors.initials: A
authors.lastname: Fortunelli
authors.forename: Luca
authors.initials: L
authors.lastname: Sementa
authors.forename: Giovanni
authors.initials: G
authors.lastname: Barcaro
authors.affiliation: §X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States.
authors.forename: Xiaobing
authors.initials: X
authors.lastname: Zuo
authors.affiliation: ∥Bruker AXS Inc., 5465 East Cheryl Parkway, Madison, Wisconsin 53711, United States.
authors.forename: Bruce C
authors.initials: BC
authors.lastname: Noll