ja070411g_si_003.cif (37 kB)

Spin Switching via Targeted Structural Distortion

Download (37 kB)
posted on 23.05.2007, 00:00 by Constantinos J. Milios, Alina Vinslava, Wolfgang Wernsdorfer, Alessandro Prescimone, Peter A. Wood, Simon Parsons, Spyros P. Perlepes, George Christou, Euan K. Brechin
The deliberate “stepwise” structural distortion of the [MnIII6O2(sao)6(O2CR)2L4] (S = 4, Ueff = 28 K) family of SMMs (where sao2- is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime and L = MeOH, EtOH) via the use of derivatized oxime ligands and bulky carboxylates leads to a family of single-molecule magnets with larger spin ground states and enhanced blocking temperatures. Replacing sao2- and HCO2- in the molecule [MnIII6O2(sao)6(O2CH)2(MeOH)4] (1), with Et-sao2- (Et-saoH2 = 2-hydroxypropiophenone oxime) and Me3CCO2- (pivalate), produces the complex [MnIII6O2(Et-sao)6(O2CCMe3)2(EtOH)5] (2) that displays an S = 7 ground state with Ueff = 30 K. Replacing Me3CCO2- with PhCO2- produces the complex [MnIII6O2(Et-sao)6(O2CPh)2(EtOH)4(H2O)2] (3) that displays an S = 12 ground state with Ueff = 53 K. The ligand substitution invokes a subtle structural distortion to the core of the molecule evidenced by an increased “twisting” of the oxime moiety (Mn−N−O−Mn) and a change in carboxylate ligation, which, in turn, invokes a dramatic change in the observed magnetic properties by switching weak antiferromagnetic exchange to weak ferromagnetic exchange.