Tracking the conical intersection dynamics for the photoinduced Jahn–Teller switch of a Mn(iii) complex

Abstract

Octahedral Mn(III) ions predominantly exhibit an axially elongated Jahn–Teller (JT) distortion, which is responsible for their large uniaxial magnetic anisotropy. As a result, they are often used in the synthesis of single-molecule magnets (SMMs). Modulation of the JT distortion using femtosecond laser pulses could offer a route to controlling the magnetisation direction, and therefore is promising for the development of data storage devices that work on ultrafast timescales. Photoinduced switching of the distortion from an axially elongated to an axially compressed structure has been demonstrated for various Mn(III) complexes. However, the dynamics around the region of the conical intersection for the photoinduced JT switch remains unclear. Here, ultrafast transient absorption spectra were recorded for solutions of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III) (Mn(dpm)₃) in ethanol to further explore the dynamics of the photoinduced JT switch. We observe the generation of a vibrational wavepacket on the excited state surface, which has a frequency of approximately 155 cm⁻¹ and encompasses a JT-active vibrational mode. This coherent motion is maintained after passage through the conical intersection back to the ground state, which launches wavepackets along the ground state potential energy surface (PES) with frequencies of approximately 180 and 110 cm⁻¹ that we assign to the elongated and compressed state, respectively. Inspection of the relative phases of the frequencies reveals phase shifts that are consistent with a one-mode reaction coordinate, and passes through the conical intersection at 1/4 and 3/4 of the excited state vibrational period. Our results provide direct insights into the non-adiabatic dynamics of Mn(III) complexes, which can be used to guide the synthesis of optically controlled SMMs.