Triangulating Dopant-Level Mn(II) Insertion in a Cs 2 NaBiCl 6 Double Perovskite Using Magnetic Resonance Spectroscopy.

Lead-free metal halide double perovskites are gaining increasing attention for optoelectronic applications. Specifically, doping metal halide double perovskites using transition metals enables broadband tailorability of the optical bandgap for these emerging semiconducting materials. One candidate material is Mn(II)-doped Cs 2 NaBiCl 6 , but the nature of Mn(II) insertion on chemical structure is poorly understood due to low Mn loading. It is critical to determine the atomic-level structure at the site of Mn(II) incorporation in doped perovskites to better understand the structure-property relationships in these materials and thus to advance their applicability to optoelectronic applications. Magnetic resonance spectroscopy is uniquely qualified to address this, and thus a comprehensive three-pronged strategy, involving solid-state nuclear magnetic resonance (NMR), high-field dynamic nuclear polarization (DNP), and electron paramagnetic resonance (EPR) spectroscopies, is used to identify the location of Mn(II) insertion in Cs 2 NaBiCl 6 . Multinuclear ( 23 Na, 35 Cl, 133 Cs, and 209 Bi) one-dimensional (1D) magnetic resonance spectra reveal a low level of Mn(II) incorporation, with select spins affected by paramagnetic relaxation enhancement (PRE) induced by Mn(II) neighbors. EPR measurements confirm the oxidation state, octahedral symmetry, and low doping levels of the Mn(II) centers. Complementary EPR and NMR measurements confirm that the cubic structure is maintained with Mn(II) incorporation at room temperature, but the structure deviates slightly from cubic symmetry at low temperatures (<30 K). HYperfine Sublevel CORrelation (HYSCORE) EPR spectroscopy explores the electron-nuclear correlations of Mn(II) with 23 Na, 133 Cs, and 35 Cl. The absence of 209 Bi correlations suggests that Bi centers are replaced by Mn(II). Endogenous DNP NMR measurements from Mn(II) → 133 Cs (<30 K) reveal that the solid effect is the dominant mechanism for DNP transfer and supports that Mn(II) is homogeneously distributed within the double-perovskite structure.