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

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• 作者：Yanfeng Bi ; Xiu-Teng Wang ; Wuping Liao ; Xinwu Wang ; Ruiping Deng ; Hongjie Zhang ; Song Gao
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：December 21, 2009
• 年：2009
• 卷：48
• 期：24
• 页码：11743-11747
• 全文大小：804K
• 年卷期：v.48,no.24(December 21, 2009)
• ISSN：1520-510X

文摘

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 (H₄PTC4A) and p-tert-butylthiacalix[4]arene (H₄TC4A). All four frameworks can be formulated as [Ln^III₄(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-Ln^III energy transfer for compounds 1−3 and H₄PTC4A is a more efficient “antenna” than H₄TC4A. 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.