Intercalation chemistry of cobalt and nickel dioxides: A facile route to new compounds containing organocations

A simple chemical method is reported for the intercalation of layered nickel or cobalt dioxide with organocations. Compounds containing anilinium, dodecyltrimethylammonium, octadecyltrimethylammonium, or distearyldimethylammonium cations are obtained by reaction of lithiated hosts with aqueous persulfate, followed by treatment with the desired organocation. Basal-repeat distances for the intercalated products indicate that the arrangements of organocations are similar to those seen with other layered hosts, with bilayers of alkylammonium ions, or a single layer of anilinium, in the pillared galleries. Thermogravimetric and elemental analyses are used to estimate compound stoichiometries, and indicate the partial exchange of organocation for lithium. The anilinium compound contains oligomeric cations, and is unstable when treated with polar solvents. Open circuit measurements indicate that the materials contain Co in an oxidation state of 3+ or higher.