Probing structural and dynamic properties of MAPbCl₃ hybrid perovskite using Mn²⁺ EPR

Hybrid methylammonium (MA) lead halide perovskites have emerged as materials exhibiting excellent photovoltaic performance related to their rich structural and dynamic properties. Here, we use multifrequency (X-, Q-, and W-band) electron paramagnetic resonance (EPR) spectroscopy of Mn2+ impurities in MAPbCl(3) to probe the structural and dynamic properties of both the organic and inorganic sublattices of this compound. The temperature dependent continuous-wave (CW) EPR experiments reveal a sudden change of the Mn2+ spin Hamiltonian parameters at the phase transition to the ordered orthorhombic phase indicating its first-order character and significant slowing down of the MA cation reorientation. Pulsed EPR experiments are employed to measure the temperature dependences of the spin-lattice relaxation T-1 and decoherence T-2 times of the Mn2+ ions in the orthorhombic phase of MAPbCl(3) revealing a coupling between the spin center and vibrations of the inorganic framework. Low-temperature electron spin echo envelope modulation (ESEEM) experiments of the protonated and deuterated MAPbCl(3) analogues show the presence of quantum rotational tunneling of the ammonium groups, allowing to accurately probe their rotational energy landscape.