Molecular and Electronic Structure of the Cluster [Au₈(PPh₃)₈](NO₃)₂

Abstract

We present a detailed structural discussion of [Au 8 (PPh 3 ) 8 ](NO 3 ) 2 , crystallized as a CH 2 Cl 2 solvate. Its structure is compared with closely related triphenylphosphine-stabilized gold clusters. Characterization by optical extinction spectroscopy, luminescence spectroscopy, voltammetry and DFT calcu-

A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

“…The wavelength is converted into energy using the equation E (eV) = 1240/ λ (nm). Simon and co‐workers measured the optical absorption of Au 11 (PPh 3 ) 7 Cl 3 and estimated the energy gap of the first electronic transition to be ≈2.0 eV, [ 25c ] which matched closely with the theoretical calculation of the simplified Au 11 (PH 3 ) 7 Cl 3 structure by Häkkinen and co‐workers. [ 173a ] The energy of other optical transitions can be estimated by deconvolution of the spectral profile.…”

“…The Au 9 (PPh 3 ) 8 (NO 3 ) 3 cluster exhibits two weak, broad PL peaks at 579 and 853 nm in the solid state. [ 25a ] A near‐IR PL peak around 1080 nm has also been observed for Au 11 (PPh 3 ) 7 Cl 3 . Heteroatom doping of Au clusters can modulate the electronic structure and thus the optical properties.…”

“…Undecagold was first reported in 1969, however the lack of precise structural determination led to several proposed formulae such as Au 11 (PPh 3 ) 7 Cl 3 , Au 11 (PPh 3 ) 8 Cl 3, and [Au 11 (PPh 3 ) 8 Cl 2 ] + until the structure was determined by Simon and co‐workers in 2013. [ 25b ] This discrepancy results from the formation of isostructural undecagold clusters, Au 11 (PPh 3 ) 7 Cl 3 and [Au 11 (PPh 3 ) 8 Cl 2 ]Cl, using the same synthetic method. [ 70 , 119 ] Recently, Hutchison and co‐workers showed that this synthetic protocol produces a mixture of Au 11 (PPh 3 ) 7 Cl 3 and [Au 11 (PPh 3 ) 8 Cl 2 ]Cl, and the separation of the components is difficult.…”

“…In particular, the work of Simon and co‐workers in reproducing some of these clusters and providing complete characterizations led to a revival in interest in gold–phosphine clusters. [ 25 ] Laskin's group utilizes mass spectrometry to investigate phosphine ligand effects in gold clusters. [ 26 ] Pettibone and Hudgens have recently made significant breakthroughs in defining the reaction pathways and mechanism in diphosphine‐ligated Au cluster systems.…”

Poly‐Hydride [AuI7(PPh3)7H5](SbF6)2 cluster complex: Structure, Transformation, and Electrocatalytic CO2 Reduction Properties

“…[16] The UV/Vis absorption spectra and crystal structure (Table S2 and Figure S14) of the final product are consistent with that of the previously reported [Au 8 (PPh 3 ) 7 ] 2 + nanocluster. [17,18] Noted that thin layer chromatography (TLC), UV/Vis, and ESI-MS were performed which revealed the mono-dispersity of Au 7 H 5 2 + nanoclusters before illumination (Figure S15).…”