Ionothermal synthesis and magnetic studies of novel two-dimensional metal-formate frameworks.

ABSTRACT

Five novel two-dimensional frameworks containing formate-bridged metal-centered octahedra are synthesized ionothermally from two ionic liquids previously unused as solvents in hybrid synthesis, 2-hydroxyethylammonium (HEA) formate, and 1-hydroxy-3-proplyammonium (HPA) formate. Templating effects of the cation from each ionic liquid drive the formation of different structures. [NH(3)C(2)H(4)OH](2)[M(CHO(2))(4)] (1 M = Co, 2 M = Ni) exhibit the same stoichiometry and connectivity as their manganese analogue (3 M = Mn), but the manganese form exhibits a different topology from 1 and 2. [NH(3)C(3)H(6)OH][M(CHO(2))(3)(H(2)O)] (4 M = Co, 5 M = Mn) were synthesized using the HPA formate ionic liquid with a metal-formate connectivity related to those of 1-3. Canted antiferromagnetic ordering occurs at low temperatures (1 T(N) = 7.0 K, 2 T(N) = 4.6 K, 3 T(N) = 8.0 K, 4 T(N) = 7.0 K, 5 T(N) = 9.2 K), similar to the magnetic properties previously reported for other metal-formate hybrid materials.