A new ground triplet biradical 2′,4′,6′-triisopropylbiphenyl-3,5-diyl bis(tert-butyl nitroxide) (iPr3BPBN) was prepared and characterized by means of room-temperature ESR spectroscopy displaying a zero-field splitting pattern together with a half-field signal. Complex formation with gadolinium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate (hfac) afforded a macrocycle [{Gd(hfac)3(μ-iPr3BPBN)}2]. As the X-ray crystallographic analysis clarified, the biradical serves as a bridging ligand, giving a 16-membered ring, where each nitroxide radical oxygen atom is directly bonded to a Gd3+ ion. The magnetic study revealed that the iPr3BPBN bridge behaved as a practically triplet biradical and that the Gd3+-radical magnetic coupling was weakly ferromagnetic. The exchange parameters were estimated as 2jrad-rad/kB > 300 K and 2JGd-rad/kB = 1.2 K in the H = −2J S1•S2 convention. The DFT calculation based on the atomic coordinates clarified the ground triplet nature in metal-free iPr3BPBN and the enhanced triplet character upon coordination. The calculation also suggests that ferromagnetic coupling would be favorable when the Gd-O-N-C(sp2) torsion comes around 100°. The present results are compatible with the proposed magneto-structure relationship on the nitroxide-Gd compounds.
