Ground-State Spin Dynamics in d¹ Kagome-Lattice Titanium Fluorides

Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH₃NH₃)₂NaTi₃F₁₂, 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH₃NH₃)₂KTi₃F₁₂, 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie-Weiss temperatures of both 1-Ti (-139.5(7) K) and 2-Ti (-83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.