An iron ketimide single-molecule magnet [Fe(4)(N[double bond, length as m-dash]CPh(2))(6)] with suppressed through-barrier relaxation

Reaction of FeBr(2) with 1.5 equiv. of LiN[double bond, length as m-dash]CPh(2) and 2 equiv. of Zn, in THF, results in the formation of the tetrametallic iron ketimide cluster [Fe(4)(N[double bond, length as m-dash]CPh(2))(6)] (1) in moderate yield. Formally, two Fe centers in 1 are Fe(i) and two are Fe(ii); however, Mössbauer spectroscopy and SQUID magnetometry suggests that the [Fe(4)](6+) core of 1 exhibits complete valence electron delocalization, with a thermally-persistent spin ground state of S = 7. AC and DC SQUID magnetometry reveals the presence of slow magnetic relaxation in 1, indicative of single-molecule magnetic (SMM) behaviour with a relaxation barrier of U(eff) = 29 cm(−1). Remarkably, very little quantum tunnelling or Raman relaxation is observed down to 1.8 K, which leads to an open hysteresis loop and long relaxation times (up to 34 s at 1.8 K and zero field and 440 s at 1.67 kOe). These results suggest that transition metal ketimide clusters represent a promising avenue to create long-lifetime single molecule magnets.