Ligand exchange reactions can introduce new ligands onto clusters to afford new physical/chemical properties and functions. Many studies on the ligand exchange reactions of thiolate-protected gold clusters using other chalcogenates (i.e., selenolates or tellurolates) as exchange ligands have been conducted in recent years. However, there is limited information on the preferential exchange sites and electronic structure of the exchanged products. In this study, we investigated the geometric and electronic structures of the products obtained by reacting [Au25(SC2H4Ph)18]− with PhSeH or (PhTe)2 by single-crystal X-ray structural analysis, differential pulse voltammetry, and optical absorption spectroscopy. The results revealed that these exchange reactions preferentially produce products containing substituted ligands close to the gold core. In addition, we quantitatively determined the changes in the redox potentials and optical transition energies induced by continuous ligand exchange. This systematic investigation revealed that exchange with SePh induces nonlinear changes in the electronic structure of the clusters with the number of exchanged ligands. These findings are expected to lead to the improved design guidelines to produce clusters with new functions by ligand exchange with other chalcogenates.

A recent study implied that a hetero-biicosahedral 25-atom cluster composed of two kinds of icosahedral 13-atom clusters could serve as a molecular rectifier and dipole material. However, no hetero-biicosahedral 25-atom clusters containing three types of ligands, in this case, phosphines, halogens, and thiolates, have been reported. In this study, we selectively synthesized [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]Cl (Au = gold, Pd = palladium, PPh3 = triphenylphosphine, SC2H4Ph = phenylethanethiolate, Cl = chloride), in which one Au was replaced with a Pd. The single-crystal X-ray structural analysis demonstrated that [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]Cl was a hetero-biicosahedral 25-atom cluster in which the central atom of one icosahedral Au13 core was replaced by a Pd atom. Optical absorption spectroscopy suggested that the electronic structure of each individual icosahedral 13-atom core in [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ was reasonably well maintained, similar to the case of [Au25(PPh3)10(SC2H4Ph)5Cl2]2+. Density functional theory calculation revealed that the peak splitting in the region below 2.2 eV of the optical absorption spectrum of [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ is due to the splitting of HOMOs and also suggested that this cluster has dipole moment. Electrochemical measurements showed that [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ was relatively stable to reduction. These results are expected to contribute to the development of molecular rectifiers and dipole materials based on hetero-biicosahedral 25-atom clusters.

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Recently, platinum (Pt) clusters have attracted attention as miniaturized fuelcell redox catalysts. Although Pt clusters can be synthesized with atomic accuracy using carbon monoxide (CO) and phosphine as ligands, few studies have examined their electronic structure. We obtained experimental information about the electronic structure of these Pt clusters. We precisely synthesized the cationic Pt 17 cluster, [Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2), protected by CO and triphenylphosphine (PPh 3 ) by a simple method and studied its geometric and electronic structures by single-crystal X-ray structure analysis, X-ray photoelectron spectroscopy, optical absorption spectroscopy, differential pulse voltammetry, and photoluminescence spectroscopy. The results indicated that cationic [Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2) has a geometric structure similar to that of previously reported neutral Pt 17 (CO) 12 (PEt 3 ) 8 . The Pt 17 skeleton of Pt 17 (CO) 12 (PPh 3 ) 8 depended on the charge state of the cluster ([Pt 17 (CO) 12 (PPh 3 ) 8 ] + or [Pt 17 (CO) 12 (PPh 3 ) 8 ] 2+ ). [Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2) possessed a discretized electronic structure, similar to that of fine gold clusters, and exhibited photoluminescence in the near-infrared region. This research will aid fundamental and applied research on Pt clusters.

Hydroxyapatite (HA) is known to be biocompatible and osteoconductive, and can be synthesized chemically. The objective of the present study is to clarify the effect of pressure during sintering on the mechanical properties of HA. HA was sintered using a hot press system at a uniaxial pressure ranging from 7.81 to 62.5 MPa at a maximum temperature of 1200 degrees C with a heating rate of 10 degrees C/min. The density of the HA increased with increasing pressure and peaked at the sintering pressure of 31.2 MPa. Four-points bending tests and fracture toughness measurements with indentation method were conducted to clarify the effect of sintering pressure. Bending strength decreased at the pressure > 31.2 MPa. This result indicates that residual stress generated during sintering process became larger with increasing pressure. Fracture toughness were also lower with high density HA.

Crack propagation behavior in 2-dimensional polycrystals is simulated and analyzed as a function of the fracture toughness of the grain boundary. The path of a crack impinging on a grain boundary is determined by the competition theory between intergranular and transgranular propagation. With decreasing boundary toughness, the tendency of intergranular propagation increases and the apparent fracture toughness of the polycrystal decreases. The results of the 2-dimensional analysis are compared with the simulation, and the advantages and limitations are discussed. The grain boundary toughness is evaluated by comparing the simulated crack paths with direct observations, resulting in a reasonable value for alumina ceramics, The fracture behavior is characterized in a macro-scale by the percentage of transgranular fracture and also in a micro-scale by the distribution of crack deflection angles.

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