We report on the computational design of star-like CBe5Au5+ cluster with planar pentacoordinate carbon (ppC), which is also classified as a superalkali cation. Relevant isovalent CBe5Aunn-4 (n = 2-4), BBe5Au5, and NBe5Au52+ clusters with ppC/B/N are studied as well. Global-minimum structures of the clusters are established via computer global searches. The species feature a pentacoordinate pentagonal XBe5 (X = C, B, N) core, with Au occupying outer bridging positions. Molecular dynamics simulations indicate that they are dynamically stable. Bonding analysis reveals 3-fold (π and σ) aromaticity in CBe5Au5+, a key concept that overrides the 18-electron rule and should be applicable for (or help revisit existing models of) other planar hypercoordinate systems. Vertical electron affinities of CBe5Au5+ and its lighter counterparts (CBe5Cu5+ and CBe5Ag5+) are calculated to be unusually low, which are below 3.89 eV, the smallest atomic ionization potential of any element in the periodic table. Thus, these three clusters belong to superalkali cations. The merge of ppC and superalkali characters makes them unique chemical species.
