Tetranuclear and Pentanuclear Compounds of the Rare-Earth Metals: Synthesis and Magnetism.

Abstract

The Schiff-base proligand 4-tert-butyl-2,6-bis-[(2-hydroxy-phenylimino)methyl]phenol (H3L) was prepared in situ from 4-tert-butyl-2,6-diformylphenol and 2-aminophenol. The proligand (H3L) was used with dibenzoylmethane (DBMH) or acetylacetone (acacH) with lanthanides giving compounds with varying arrangements of metal atoms and nuclearities. The tetranuclear compound {[Dy4(L)3(DBM)4][Et3NH]} (1) and pentanuclear compound {[Dy5(μ3-OH)2(L)3(DBM)4(MeOH)4]·4(MeOH)} (2) were obtained from the ligand (L)(3-) and dibenzoylmethane. The tetranuclear compounds {[Dy4(μ4-OH)(L)2(acac)4(MeOH)2(EtOH)(H2O)]·(NO3)·2(MeOH)·3(EtOH)} (3) and {[Ln4(μ3-OH)2(L)(HL)(acac)5(H2O)] (HNEt3)(NO3)·2(Et2O)} (Ln = Tb (4), Dy (5), Ho (6), and Tm (7)) resulted when the ligand (L)(3-) was used in the presence of acetylacetone. In the solid state structures, the tetranuclear compound 1 adopts a linear arrangement of metal atoms, while tetranuclear compound 3 has a square grid arrangement of metal atoms, and tetranuclear compounds 4-7 have a seesaw-shaped arrangement of metal atoms. The composition found from single-crystal X-ray analysis of compound 1 and 3-7 is supported by electrospray ionization mass spectrometry (ESI-MS). The magnetic studies on compounds 1 suggest the presence of weak ferromagnetic interactions, whereas compounds 2-6 exhibit weak antiferromagnetic interactions between neighboring metal centers. Compounds 1, 2, and 3 also show single-molecule magnet behavior under an applied dc field.