We report the total structure of Au(38)(SC(2)H(4)Ph)(24) nanoparticles determined by single crystal X-ray crystallography. This nanoparticle is based upon a face-fused Au(23) biicosahedral core, which is further capped by three monomeric Au(SR)(2) staples at the waist of the Au(23) rod and six dimeric staples with three on the top icosahedron and other three on the bottom icosahedron. The six Au(2)(SR)(3) staples are arranged in a staggered configuration, and the Au(38)S(24) framework has a C(3) rotation axis.

We report a solution-phase conversion process of the [Au25(SCH2CH2Ph)18]− anionic cluster into a charge neutral cluster [Au25(SCH2CH2Ph)18]0 via air oxidation. The one-electron loss of the Au25 − cluster and conversion to Au25 0 is a surprise in light of the chemical inertness of gold nanoparticles. In contrast with the crystal structure of the anion cluster Au25 − , which exhibits apparent structural distortions in the Au25S18 framework, such distortions are not observed in the neutral cluster. The cluster charge effect is also manifested in the optical absorption spectra of the clusters. Given the only recently reported structure of the parent Au25 − cluster, it is of substantial interest whether its one-electron oxidized product is similar to that of Au25 −. This work unambiguously determined the structure of the one-electron oxidized product and correlates the structure with the optical properties.

Recent work towards the production of hydrogen via reduction of protons is described. Most of the systems examined in this perspective use a molecular chromophore for harvesting visible light, a catalyst, which is reduced by the excited (or reduced) chromophore, and finally a sacrificial electron source to oxidatively or reductively quench the chromophore. The reduced catalyst is then responsible for the reduction of protons resulting in hydrogen evolution. Relevant mechanistic work on this topic is also discussed.