A Series of Bimetallic Ammonium AlNa Formates

A series of AlNa bimetallic ammonium metal formate frameworks (AlNa AMFFs) have been prepared by employing various ammoniums from NH₄⁺ to large linear polyammoniums. The series consists of six perovskites of (4¹² ⋅6³ ) topology for mono-ammoniums, two chiral (4⁹ ⋅6⁶ ) frameworks incorporating polyethylene ammoniums, two niccolites with (4¹² ⋅6³ )(4⁹ ⋅6⁶ ) topology containing diammoniums, and two layered compounds made of 2D (4,4) AlNa formate sheets intercalated by small diammoniums. The first ten compounds present the structural hierarchy of (4¹² ⋅6³ )_m (4⁹ ⋅6⁶ )_n framework topologies for (m, n)=(1, 0), (0, 1), and (1, 1), respectively, in parallel to the homometallic AMFFs for divalent metals. The symmetry lowering, asymmetric formate bridges, and different hydrogen-bonding strengths appeared in the bimetallic structures owing to the different charge and size of Al³⁺ and Na⁺ seemingly inhibits the occurrence of phase transitions for more than half the AlNa AMFFs within the series, and the bimetallic members undergoing phase transitions show different transition behaviors and dielectric properties compared with the homometallic analogs. Anisotropic/negative/zero thermal expansions of the materials could be rationally attributed to the librational motion, or flip movement between different sites, of the ammonium cations, and the coupled change of AlNa formate frameworks. The thermal and IR spectroscopic properties have also been investigated.