Multiple-decker and ring sandwich formation of manganese-benzene organometallic cluster anions: Mn_{: n}Bz_n^- (n = 1-5 and 18)

Organometallic multiple-decker sandwich clusters are topics of great interest due to their unique electronic and magnetic properties originating from anisotropic structures. We report a joint anion photoelectron spectroscopic and computational study on a new family of manganese (Mn)-benzene (Bz) anionic clusters Mn_nBz_n^-. In stark contrast to the most widely studied vanadium-Bz sandwich clusters, it is found that Mn_nBz_n^- (n = 1-5) clusters exhibit unprecedented multiple-decker structures with a tilted Mn-Bz stacking and a monotonically increasing behavior of their high spin multiplicities. Furthermore, a couple of closed ring forms of Mn₁₈Bz₁₈^- and its neutral state are computationally anticipated as an intriguing "cluster of Mn₁Bz₁ clusters" in which the neutral Mn₁₈Bz₁₈ has extremely high C_18h symmetry with an uncommon spin state of 2S + 1 = 55. The extensively delocalized electron environment of Mn₁₈Bz₁₈ allows the simple Hückel model to reveal the strong intra-atomic exchange interactions within the Mn 3d electrons.