title: Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.
abstract: Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.
authors.affiliation: Graduate School of Material Science, University of Hyogo , 3-2-1 Koto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Yao
authors.affiliation: Graduate School of Material Science, University of Hyogo , 3-2-1 Koto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan.
authors.forename: Mana
authors.initials: M
authors.lastname: Iwatsu