RESUMEN
Geometric structures of free iridium cluster anions, Irn-, were examined by means of ion mobility mass spectrometry and density functional theory calculation for n = 3-15 with the additional help of photoelectron spectroscopy for n = 4-10. It has been revealed that Irn- clusters with n ≥ 5 favor a square facet and take a cubic motif in contrast to the face-centered cubic structures in the corresponding nanoparticles and bulk. A growth sequence of Irn- for n = 5-15 is proposed: single Ir atoms are sequentially attached to one side of the square plane of Ir4- to form a cubic Ir8-, and are then continuously attached on one of the square facets of Ir8- for n = 9-12 and Ir12- for n = 13-15.
RESUMEN
Atomically precise Au and Ag clusters protected by organic ligands can be viewed as chemically modified Au/Ag superatoms and have attracted interest as promising building units of functional materials and ideal platforms for studying the size-dependent evolution of structures and properties. Their structures, stability, and physicochemical properties have been characterized in solution and solid (or crystalline) phases by various methods conventionally used in materials science. However, novel and complementary information on their intrinsic stability and structures can be obtained by applying a variety of gas-phase methods, including mass spectrometry, ion mobility mass spectrometry, collision- or surface-induced dissociation mass spectrometry, photoelectron spectroscopy, and photodissociation mass spectrometry, to the chemically modified Au/Ag superatoms isolated in the gas phase. This perspective describes our recent efforts in the gas-phase studies on chemically synthesized Au/Ag superatoms.
RESUMEN
Magic-number gold nanoclusters are atomically precise nanomaterials that have enabled unprecedented insight into structure-property relationships in nanoscience. Thiolates are the most common ligand, binding to the cluster via a staple motif in which only central gold atoms are in the metallic state. The lack of other strongly bound ligands for nanoclusters with different bonding modes has been a significant limitation in the field. Here, we report a previously unknown ligand for gold(0) nanoclusters-N-heterocyclic carbenes (NHCs)-which feature a robust metal-carbon single bond and impart high stability to the corresponding gold cluster. The addition of a single NHC to gold nanoclusters results in significantly improved stability and catalytic properties in the electrocatalytic reduction of CO2. By varying the conditions, nature and number of equivalents of the NHC, predominantly or exclusively monosubstituted NHC-functionalized clusters result. Clusters can also be obtained with up to five NHCs, as a mixture of species.
RESUMEN
We herein investigated collision-induced dissociation (CID) processes of undecagold clusters protected by mixed ligands [Au11(PPh3)8X2]+ (X = Cl, C≡CPh) using mass spectrometry and density functional theory calculations. The results showed that the CID produced fragment ions [Au x (PPh3) y X z ]+ with a formal electron count of eight via sequential loss of PPh3 ligands and AuX(PPh3) units in a competitive manner, indicating that the CID channels are governed by the electronic stability of the fragments. Interestingly, the branching fraction of the loss of the AuX(PPh3) units was significantly smaller for X = C≡CPh than that for X = Cl. We ascribed the effect of X on the branching fractions of dissociations of PPh3 and AuX(PPh3) to the steric difference.