Aromaticity is a concept invented to account for the unusual stability of a
n important class of organic molecules: the aromatic compounds. Here we rep
ort experimental and theoretical evidence of aromaticity in all-metal syste
ms. A series of bimetallic clusters with chemical composition MAl4- (M = Li
, Na, or Cu), was created and studied with photoelectron spectroscopy and a
b initio calculations. All the MAl4- species possess a pyramidal structure
containing an M+ cation interacting with a square Al-4(2-) unit. Ab initio
studies indicate that Al-4(2-) exhibits characteristics of aromaticity with
two delocalized pi electrons (thus following the 4n + 2 electron counting
rule) and a square planar structure and maintains its structural and electr
onic features in all the MAl4- complexes. These findings expand the aromati
city concept into the arena of all-metal species.