Transition metal redox switches for reversible "on/off" and "slow/fast" single-molecule magnet behaviour in dysprosium and erbium bis-diamidoferrocene complexes. Academic Article uri icon


  • Single-molecule magnets (SMMs) are considered viable candidates for next-generation data storage and quantum computing. Systems featuring switchability of their magnetization dynamics are particularly interesting with respect to accessing more complex logic gates and device architectures. Here we show that transition metal based redox events can be exploited to enable reversible switchability of slow magnetic relaxation of magnetically anisotropic lanthanide ions. Specifically, we report anionic homoleptic bis-diamidoferrocene complexes of Dy3+ (oblate) and Er3+ (prolate) which can be reversibly oxidized by one electron to yield their respective charge neutral redox partners (Dy: [1]- , 1; Er: [2]- , 2). Importantly, compounds 1 and 2 are thermally stable which allowed for detailed studies of their magnetization dynamics. We show that the Dy3+[1]- /1 system can function as an "on"/"off" or a "slow"/"fast" redox switchable SMM system in the absence or presence of applied dc fields, respectively. The Er3+ based [2]- /2 system features "on"/"off" switchability of SMM properties in the presence of applied fields. Results from electrochemical investigations, UV-vis-NIR spectroscopy, and 57Fe Mssbauer spectroscopy indicate the presence of significant electronic communication between the mixed-valent Fe ions in 1 and 2 in both solution and solid state. This comparative evaluation of redox-switchable magnetization dynamics in low coordinate lanthanide complexes may be used as a potential blueprint toward the development of future switchable magnetic materials.

published proceedings

  • Chem Sci

author list (cited authors)

  • Dickie, C. M., Laughlin, A. L., Wofford, J. D., Bhuvanesh, N. S., & Nippe, M.

publication date

  • January 1, 2017 11:11 AM