Two dinuclear GdIII clusters based on isobutyric acid and nicotinic acid with large magnetocaloric effects

Two dinuclear GdIII cluster complexes with the formulas [Gd2(iba)6(bipy)2] (1) and [Gd2(nic)6(H2O)4] (2) (Hiba = isobutyric acid, Hnic = nicotinic acid and bipy = 2,2´-bipyridine) have been constructed by using gadolinium oxide as GdIII ion source under hydrothermal conditions. Although both 1 and 2 exhibit dinuclear structures, the coordination fashions are totally different. In 1, the carboxylate groups of Hiba take syn-syn-μ2-η1:η1, syn-syn-μ2-η1:η2 and syn-μ-η1:η1 modes and bipy acts as the chelating ligand. While the carboxylate groups of Hnic display syn-syn-μ2-η1:η1 and syn-μ-η1:η1 modes in 2 and two water molecules take part in coordination. Magnetic studies reveal weak ferromagnetic couplings and significant magnetic entropy changes with −ΔSmmax = 29.3 J kg−1 K−1 and 27.4 J kg−1 K−1 (ΔH = 7 T), respectively.