Al Cluster Superatoms as Halogens in Polyhalides and as Alkaline Earths in Iodide Salts

Abstract

Two classes of gas-phase aluminum-iodine clusters have been identified whose stability and reactivity can be understood in terms of the spherical shell jellium model. Experimental reactivity studies show that the Al 13 I – x clusters exhibit pronounced stability for even numbers of I atoms. Theoretical investigations reveal that the enhanced stability is associated with complementary pairs of I atoms occupying the on-top sites on the opposing Al atoms of the Al 13 – core. We also report the existence of another series, Al 14 I – x , that exhibits stability for odd numbers of I atoms. This series can be described as consisting of an Al 14 I – 3 core upon which the I atoms occupy on-top locations around the Al atoms. The potential synthetic utility of superatom chemistry built upon these motifs is addressed.