Thiacalix[4]arene‐Supported Tetranuclear TbIII and EuIII Compounds: Synthesis, Structure, Luminescence, and Magnetism.

Two tetranuclear compounds [Ln4Na(μ4‐OH)(TC4A)2(acac)4] [Ln = Tb (1), Eu (2)] (acac = acetylacetonate) were synthesized and characterized based on p‐tert‐butylthiacalix[4]arene (H4TC4A). Compounds 1 and 2 are isostructural and crystallize in the monoclinic C2/c space group. There are two crystallographically independent metal atoms in one asymmetric unit. Ln1, Ln2, and two metal atoms generated by the symmetry operation are bridged by one μ4‐OH group to form a planar tetragonal Ln4(μ4‐OH) unit. Each Ln4(μ4‐OH) unit is surrounded by four acac anions and two disordered sodium ions in the planar direction. The upper and lower positions of the Ln4(μ4‐OH) unit are further coordinated by two cone‐shaped TC4A ligands to form a sandwich‐type molecular structure. Luminescent measurements reveal that both compounds 1 and 2 exhibit good photoluminescent properties. Moreover, the static and dynamic magnetic properties of compound 1 were also investigated, which demonstrates that 1 is one functional material candidate combining luminescent and antiferromagnetic properties in one molecule. [ABSTRACT FROM AUTHOR]