Implications of coordination chemistry to cationic interactions in honeycomb layered nickel tellurates

• Published in: Computational materials science 2022-05, Vol.207, p.111322, Article 111322
• Main Authors: Tada, Kohei, Masese, Titus, Kanyolo, Godwill Mbiti
• Format: Article
• Language: English
• Subjects: Coordination chemistry; Density functional theory; Honeycomb layered frameworks; Metallophilic interactions; Monolayer-bilayer phase transition
• ISSN: 0927-0256; 1879-0801
• DOI: 10.1016/j.commatsci.2022.111322

Rendition: The honeycomb lattice of cations in A2Ni2TeO6 and their respective coordinations with oxygen atoms as found by Density Functional Theory (DFT) calculations. [Display omitted] •Density-functional theory calculations for A2Ni2TeO6 (A = Rb, Cs, H, Cu, Ag and Au).•Na, Rb and Cs form a prismatic coordination while Li forms octahedral coordination with oxygen atoms.•Coinage-metal atoms (Cu, Ag and Au) form a linear coordination with oxygen atoms at intermediate interlayer distances.•Hydrogen atoms form linear coordinations with oxygen atoms forming hydroxyl radical groups.•A linear coordination, coupled with the presence of metallophilic bonds, offers a possibility for novel cationic structures (such as bilayers) in honeycomb layered frameworks. Honeycomb layered tellurates represent a burgeoning class of multi-functional materials with fascinating crystal-structural versatility and a rich composition space. Despite their multifold capabilities, their compositional diversity remains underexplored due to complexities in experimental design and syntheses. Thus, in a bid to expand this frontier and derive relevant insights into allowed metastable compositions, we employ a density functional theory (DFT) approach to predict in silico the crystal structures of new honeycomb layered tellurates embodied by the composition, A2Ni2TeO6 (A = alkali, hydrogen or coinage-metal cations). Here, alkali-metal atoms with vastly larger radii than K (for instance, Rb and Cs) are found to engender a prismatic coordination with the oxygen atoms from the honeycomb slabs whilst coinage-metal atoms (such as Ag, Au and Cu) display a propensity for linear coordination. Further, H2Ni2TeO6 is found to also render a linear coordination wherein the hydrogen atom preferentially establishes a stronger coordination with one of the oxygen atoms to form hydroxyl groups. All A cations in the studied A2Ni2TeO6 compositions form a honeycomb lattice. Conclusions on the possibility of a monolayer-bilayer phase transition in coinage metal atom tellurates can be drawn by considering the implications of conformal symmetry of the cation honeycomb lattice and metallophilicity. This work not only propounds new honeycomb layered tellurate compositions but also provides novel insight into the rational design of multifunctional materials for applications ranging from energy storage, catalysis and optics to analogue condensed matter systems of gravity.