Reversible M-M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds.

The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M dimeric complexes with M-M bonding, [M (en) ] , (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor-type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en) ] . Here, the facile interconversion between dimeric-M and monomeric-M intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X-ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M (en) ] or [M(en) ] guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M-M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M →M reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.