We synthesized the novel adduct-type organic ionic crystal [C3mim][SCN·B(C6F5)3] (1) by the reaction of 1–methyl–3–propylimidazolium thiocyanate ([C3mim][SCN]), which is a room temperature ionic liquid, and B(C6F5)3, a bulky Lewis acid. The formation of a coordinative B–N bond between the SCN anion and the B(C6F5)3 in 1 was revealed by single-crystal X-ray diffractometry. We showed that 1 displays ionic conductivity in the crystalline state and that doping 1 with sodium thiocyanate and B(C6F5)3 results in a dramatic increase in ionic conductivity compared to that of 1.

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