Equatorial restriction of the photoinduced Jahn-Teller switch in Mn(iii)-cyclam complexes

Ultrafast transient absorption spectra were recorded for solutions of [Mn^III(cyclam)(H₂O)(OTf)][OTf]₂ (cyclam = 1,4,8,11-tetraazacyclotetradecane and OTf = trifluoromethanesulfonate) in water to explore the possibility to restrict the equatorial expansion following photoexcitation of the d ← d electronic transition, often resulting in a switch from axial to equatorial Jahn-Teller distortion in Mn^III complexes. Strong oscillations were observed in the excited state absorption signal and were attributed to an excited state wavepacket. The structural rigidity of the cyclam ligand causes a complex reaction coordinate with frequencies of 333, 368, 454 and 517 cm^-1, and a significantly shorter compressed-state lifetime compared to other Mn^III complexes with less restricted equatorial ligands. Complementary density functional theory quantum chemistry calculations indicate a switch from an axially elongated to a compressed structure in the first excited quintet state Q₁, which is accompanied by a modulation of the axial tilt angle. Computed harmonic frequencies for the axial stretching mode (∼379 cm^-1) and the equatorial expansions (∼410 and 503 cm^-1) of the Q₁ state agree well with the observed coherences and indicate that the axial bond length contraction is significantly larger than the equatorial expansion, which implies a successful restriction of the wavepacket motion. The weak oscillation observed around 517 cm^-1 is assigned to a see-saw motion of the axial tilt (predicted ∼610 cm^-1). The results provide insights into the structural perturbations to the molecular evolution along excited state potential energy surfaces of Mn^III octahedral complexes and can be used to guide the synthesis of optically controlled Mn^III-based single-molecule magnets.