Lanthanide Anionic Metal鈥揙rganic Frameworks Containing Semirigid Tetracarboxylate Ligands: Structure, Photoluminescence, and Magnetism

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• 作者：Shengqun Su ; Wan Chen ; Chao Qin ; Shuyan Song ; Zhiyong Guo ; Guanghua Li ; Xuezhi Song ; Min Zhu ; Song Wang ; Zhaomin Hao ; Hongjie Zhang
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：April 4, 2012
• 年：2012
• 卷：12
• 期：4
• 页码：1808-1815
• 全文大小：545K
• 年卷期：v.12,no.4(April 4, 2012)
• ISSN：1528-7505

文摘

A series of lanthanide anionic metal鈥搊rganic frameworks, [NH₂(CH₃)₂][Ln(MDIP)(H₂O)] (Ln = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7); H₄MDIP = methylenediisophthalic acid) and [NH₂(CH₃)₂][Ln(MDIP)(H₂O)]路0.5NH(CH₃)₂ (Ln = Er (8), Tm (9), Yb (10)), have been synthesized and characterized. In compounds 1鈥?b>7, the adjacent Ln³⁺ ions are intraconnected to form infinite metal-carboxylate oxygen chain-shaped building blocks along the [001] direction. In compounds 8鈥?b>10, MDIP ligands bridge dinuclear lanthanide centers to form three-dimensional frameworks which can be rationalized as a (4,8)-connected topological net with the Schl盲fli symbol of (4¹⁰.6¹⁴.8⁴)(4⁵.6)₂. Dimethylamine cations occupy the vacancy of all the compounds as counterions. The photophysical properties of trivalent Pr, Nd, Sm, Eu, Tb, Dy, Er, Yb compounds at room temperature were investigated and showed that MDIP is an efficient sensitizer of the luminescence of both the Tb³⁺ ion emitting visible light and the Yb³⁺ ion emitting in the near-IR. Antiferromagnetic interactions between Gd³⁺ ions were observed from magnetic susceptibility data.