Exchange interactions at the origin of slow relaxation of the magnetization in {TbCu3} and {DyCu3} single-molecule magnets

New {TbCu3} and {DyCu3} single-molecule magnets (SMMs) containing a low-symmetry LnIII center (shape measurements relative to a trigonal dodecahedron and biaugmented trigonal prism are 2.2-2.3) surrounded by three CuII metalloligands are reported. SMM behavior is confirmed by frequency-dependent out-of-phase ac susceptibility signals and single-crystal temperature and sweep rate dependent hysteresis loops. The ferromagnetic exchange interactions between the central LnIII ion and the three CuII ions could be accurately measured by inelastic neutron scattering (INS) spectroscopy and modeled effectively. The excitations observed by INS correspond to flipping of CuII spins and appear at energies similar to the thermodynamic barrier for relaxation of the magnetization, ∼15-20 K, and are thus at the origin of the SMM behavior. The magnetic quantum number Mtot of the cluster ground state of {DyCu3} is an integer, whereas it is a half-integer for {TbCu3}, which explains their vastly different quantum tunneling of the magnetization behavior despite similarThe research leading to these results has received funding from the UK Engineering and Physical Sciences Research Council (grant ref EP/I027203/1) and the European Community’s Seventh Framework Programme (FP7/2007-2013) under grant agreement No. 290605 (PSI-FELLOW/COFUND). This work is partially based on experiments performed at the Swiss spallation neutron source SINQ, Paul Scherrer Institute, Villigen, Switzerland