Synthesis and density functional calculations of the new molecule-based magnet precursor [Fe(H2opba-i)(dmso)2]Cl

Abstract

A new precursor of molecule-based magnetic systems, [Fe(H2opba-i)(dmso)2]Cl (1), with opba = ortho-phenylenebis(oxamato) in an iminoalcohol tautomeric form, was obtained as a product from the reaction between H4opba and FeCl3. Data from elemental analysis, IR and Mossbauer spectroscopies and magnetic measurements indicate that this precursor is composed of a mixture of trans (83 percent) and cis (17percent) isomers. The XMT value at 298K (2.1 emu K mol-1) corresponds to FeIII with spin state (S) between 3/2 and 5/2. Theoretical calculations (PBE/DZVP2) of trans- and cis-[Fe(H2opba-i)(dmso)2]+ show that both isomers have spin S = 1/2 in the ground state and S = 3/2 for the trans and S = 5/2 for the cis in the first excited state. The combination of these results leads to XMT values of 0.375 and 2.3 emu K mol-1, at low and high temperature respectively, which are in accordance with the experimental data for 1.