Borohydrides: from sheet to framework topologies

Abstract

The five novel compounds ALiM(BH4)4 (A = K or Rb; M = Mg or Mn) and K3Li2Mg2(BH4)9 crystallizing in the space groups Aba2 and P2/c, respectively, represent the first two-dimensional topologies amongst homoleptic borohydrides. The crystal structures have been solved, refined and characterized by synchrotron X-ray powder diffraction, neutron powder diffraction and solid-state DFT calculations. Minimal energies of ordered models corroborate crystal symmetries retrieved from diffraction data. The layered Li-Mg substructure forms negatively charged uninodal 4-connected networks. It is shown that this connectivity cannot generate the long sought-after, bimetallic Li-Mg borohydrides without countercations when assuming preferred coordination polyhedra as found in Mg(BH4)2 and LiBH4. The general properties of the trimetallic compound series are analogous with the anhydrous aluminosilicates. Additionally, a relationship with zeolites is suggested, which are built from three-dimensional Al-Si-O networks with a negative charge on them. The ternary metal borohydride systems are of interest due to their potential as novel hydridic frameworks and will allow exploration of the structural chemistry of light-metal systems otherwise subject to eutectic melting.