Single-molecule magnet behavior and magnetocaloric effect in ferromagnetically coupled Ln(III)-Ni(II)-Ni(II)-Ln(III)...

New types of linear tetranuclear Ln(III)-Ni(II)-Ni(II)-Ln(III) (Ln(III) = Dy (1), Gd (2)) complexes have been prepared using the multidentate ligand N,N'-bis(3-methoxysalicylidene)-1,3-diaminobenzene, which has two sets of NO and OO' coordination pockets that are able to selectively accommodate Ni(II) and Ln(III) ions, respectively. The X-ray structure analysis reveals that the Ni(II) ions are bridged by phenylenediimine groups forming a 12-membered metallacycle in the central body of the complex, whereas the Ln(III) ions are located at both sides of the metallacycle and linked to the Ni(II) ions by diphenoxo bridging groups. Phenylenediimine and diphenoxo bridging groups transmit ferromagnetic exchange interactions between the two Ni(II) ions and between the Ni(II) and the Ln(III) ions, respectively. Complex 1 shows slow relaxation of the magnetization at zero field and a thermal energy barrier Ueff = 7.4 K with HDC = 1000 Oe, whereas complex 2 exhibits an S = 9 ground state and significant magnetocaloric effect (-ΔSm = 18.5 J kg(-1) K(-1) at T = 3 K and ΔB = 5 T).