Thiacalix[4]arene-Supported Planar Ln4 (Ln = TbIII, DyIII) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient antenna than H(4)TC4A. The Dy-III compounds exhibit slow magnetic relaxation behavior of single-molecule magnet nature. The substitution of the t-Bu group with a phenyl group at the up-rim of thiacalix[4]arene leads to different extended structures and physical properties of as-synthesized compounds.