Electronic properties of transition metal-benzene sandwich clusters

Organometallic clusters composed of transition metal atoms and benzene molecules have been topics of great interest from both fundamental and technological points of view. In this chapter, we review the progress in the physical chemistry of transition metal-benzene clusters. The intrinsic properties of transition metal-benzene clusters as a function of cluster size are investigated by gasphase experiments, often in combination with quantum chemical calculations. In particular, vanadium-benzene clusters denoted V_nBz_m, showing magic numbers at m = n + 1, n, and n – 1, are characterized to possess multiple-decker sandwich structures, where vanadium atoms and benzene molecules are alternately piled up. Moreover, the discovery of such multiple-decker formation is a cornerstone in bottom-up approaches of molecular magnetism. The interplay of mass spectrometry, laser spectroscopies, and density functional calculations reveals that multiple-decker V_nBz_m clusters exhibit monotonic increase in magnetic moment with the number of layers. Anion photoelectron spectroscopic studies allow direct observations of the geometric and electronic structures of sandwich clusters and their anions. Major progress in this direction includes the recent characterization of tilted multipledecker sandwich cluster anions composed of manganese atoms and benzene molecules. The sandwich clusters with high-spin characteristics will hopefully be exploited as building blocks in advanced electronic and magnetic nanomaterials via controlled assembly.