New Family of Lanthanide-Based Inorganic鈥揙rganic Hybrid Frameworks: Ln2(OH)4[O3S(CH2)nSO3]路2H2O (Ln = La, Ce, Pr, Nd

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• 作者：Jianbo Liang ; Renzhi Ma ; Yasuo Ebina ; Fengxia Geng ; Takayoshi Sasaki
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 18, 2013
• 年：2013
• 卷：52
• 期：4
• 页码：1755-1761
• 全文大小：473K
• 年卷期：v.52,no.4(February 18, 2013)
• ISSN：1520-510X

文摘

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic鈥搊rganic hybrid frameworks, Ln₂(OH)₄[O₃S(CH₂)_nSO₃]路2H₂O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln³⁺ ions from a solution containing 伪,蠅-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)₂(H₂O)]⁺}_{鈭?/sub> layers, which are cross-linked by 伪,蠅-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl3-type Ln(OH)3 involving penetration of organic chains into two {LnO9} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO9} polyhedra. A new hybrid oxide, Ln2O2[O3S(CH2)nSO3], which is supposed to consist of alternating {[Ln2O2]²⁺}鈭?/sub> layers and 伪,蠅-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.}