Origin of Weak Magnetic Coupling in a Dimanganese(II) Complex Bridged by the Tetrathiafulvalene-Tetrathiolate Radical.

Magnetic exchange coupling ( J ) between different spin centers plays a crucial role in molecule-based magnetic materials. Direct exchange coupling between an organic radical and a metal is frequently stronger than superexchange through diamagnetic ligands, and the strategy of using organic radicals to engender desirable magnetic properties has been an area of active investigation. Despite significant advances and exciting bulk properties, the magnitude of J for radical linkers bridging paramagnetic centers is still difficult to rationally predict. It is thus important to elucidate the features of organic radicals that govern this parameter. Here, we measure J for the tetrathiafulvalene-tetrathiolate radical (TTFtt 3-• ) in a dinuclear Mn(II) complex. Magnetometry studies show that the antiferromagnetic coupling in this complex is much weaker than that in related Mn(II)-radical compounds, in contrast to what might be expected for the S-based chelating donor atoms of TTFtt. Experimental and computational analyses suggest that this small J coupling may be attributed to poor overlap between Mn- and TTFtt-based magnetic orbitals coupled with insignificant spin density on the coordinating S-atoms. These factors override any expected increase in J from the comparatively strong S-donors. This work elucidates the magnetic coupling properties of the TTFtt 3-• radical for the first time and also demonstrates how multiple competing factors must be considered in rationally designing organic radical ligands for molecular-based magnetic compounds.