Magnetic coupling interaction-related photoluminescence behaviors in all-inorganic manganese chloride perovskites

Manganese halides, as dilute magnetic semiconductor materials, have magnetic coupling interactions that play an essential role in their photoluminescence (PL); however, such interactions remain controversial. AMnCl3 (AMC, A = K, Rb, and Cs) and their hydrates AMnCl3·2H2O (AMCH, A = K, Rb, and Cs) are both in the ABX3 configuration but exhibit a wide variety of structures with different connectivity types and dimensions. Their magnetic coupling interaction has been demonstrated. However, few studies have systematically investigated the PL in conjunction with the magnetic coupling interaction over these chloride compounds. In this paper, the effect of the magnetic coupling interaction on AMC and AMCH PL is mainly revealed by temperature-dependent PL spectra and lifetimes. The MnX6 (X6 = Cl4(H2O)2 or Cl6) cluster connection types affect the Mn2+–Mn2+ distances. The magnetic coupling interaction between MnX6 octahedrons affects the radiative transitions of manganese chlorides, which is influenced by the Mn2+–Mn2+ distance, local symmetry, and water ligand. The Mn2+–Mn2+ distance and the magnetic coupling interaction also affect their lifetimes. Variations in magnetic coupling interactions can shift emission wavelength, especially dual-emissions and near-infrared (NIR) emission at lower temperatures while A+ = K+. This work helps researchers understand the optical process of Mn2+ ions in different manganese compounds and provides new insights into the design of tailored Mn2+ ion phosphors.