Thiacalix[4]arene‐Supported Tetranuclear Tb^III and Eu^III Compounds: Synthesis, Structure, Luminescence, and Magnetism

Abstract

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.

Effect of single variable factor of electron‐acceptor on the luminescence quantum yield of terbium complex

“…7 F J (J = 3-6) transitions of Tb 3 + (Figure 3a, 3b). [33] The 5 D 4 ! 7 F 5 transition (543 nm) that used to monitor decay lifetimes showed a single-photon attenuation pattern, [34] with relative long fluorescence lifetime of 0.782 and 0.424 ms for Tb-Br and Tb-I (Figure 3d).…”

Constructing [CoII6] hexagon-centered heterometallic {Ln6Co6} (Ln = Y, Eu and Dy) clusters with a calix[8]arene ligand

“…For example, Dalgarno and Brechin [4][5][6][7] applied methylene-bridged calix [4]arene in the construction of SMMs and magnetic coolers. We 8,9 and others [10][11][12][13] used thia-and sulfonyl-bridged calix [4]arenes for the preparation of polynuclear clusters possessing interesting magnetic properties. However, to the best of our knowledge, polynuclear clusters based on larger calixarenes such as p-tert-butylcalix [8] arene with SMM properties and ferromagnetic ordering behaviours are rare.…”