Introduction of ester and amido functions in tetrairon(III) single-molecule magnets: synthesis and physical characterization.
Tetrairon(III) complexes with a propeller-like structure derived from [Fe(4)(OMe)(6)(dpm)(6)] (1) (Hdpm = 2,2,6,6-tetramethylheptane-3,5-dione) are providing a growing class of Single Molecule Magnets (SMMs) displaying unprecedented synthetic flexibility and ease of functionalization. Herein we report the synthesis, crystal structures and magnetic properties of two novel tetrairon(III) SMMs, [Fe(4)(esterC5)(2)(dpm)(6)] (2) and [Fe(4)(amideC5)(2)(dpm)(6)].Et(2)O.4MeOH (3.Et(2)O.4MeOH), in which functionalization of the cluster core is achieved using ester and amido linkages, respectively. To this aim, two new tripodal ligands were prepared by acylation of pentaerythritol (2,2-bis(hydroxymethyl)propane-1,3-diol) and TRIS (2-amino-2-(hydroxymethyl)propane-1,3-diol), namely H(3)esterC5 = RC(O)OCH(2)C(CH(2)OH)(3) and H(3)amideC5 = RC(O)NHC(CH(2)OH)(3) with R = n-butyl. The compounds were structurally investigated by single-crystal XRD, which demonstrated coordination of the tripodal ligands to the cluster core. The products display SMM behavior with anisotropy barriers U(eff)/k(B) congruent with 11 K due to a high-spin (S = 5) ground state and an easy axis anisotropy, described by D = -0.421 cm(-1) in 2 and -0.414 cm(-1) in 3.Et(2)O.4MeOH. The departure of U(eff) from the total splitting of the S = 5 ground multiplet, U/k(B) congruent with 15 K, has to be ascribed to the sizeable rhombic anisotropy that characterizes the two compounds (E = 0.021 cm(-1) in 2 and 0.019 cm(-1) in 3.Et(2)O.4MeOH), as confirmed by master matrix calculations of the temperature-dependent relaxation time.
Department of Chemistry & INSTM research unit, University of Modena and Reggio Emilia, Via G. Campi 183, 41100, Modena, Italy.
Maria Jesus
MJ
Rodriguez-Douton
Andrea
A
Cornia
Roberta
R
Sessoli
Lorenzo
L
Sorace
Anne-Laure
AL
Barra