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

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 Al13I –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 Al13– core. We also report the existence of another series, Al14I –x, that exhibits stability for odd numbers of I atoms. This series can be described as consisting of an Al14I –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.

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