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

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Abstract
This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear TbIII (1 and 3) and DyIII (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H4PTC4A) and p-tert-butylthiacalix[4]arene (H4TC4A). All four frameworks can be formulated as [LnIII4(PTC4A/TC4A)2(μ4-OH)Cl3(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 (μ4-OH)Ln4 cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-LnIII energy transfer for compounds 1−3 and H4PTC4A is a more efficient “antenna” than H4TC4A. The DyIII 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.

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