Rare Earth Arenedisulfonate Metal-Organic Frameworks: An Approach toward Polyhedral Diversity and Variety of Functional Compounds
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- 作者：Felipe Gá ; ndara ; Alberto Garcí ; a-Corté ; s ; Concepció ; n Cascales ; Berta Gó ; mez-Lor ; Enrique Gutié ; rrez-Puebla ; Marta Iglesias ; Angeles Monge ; Natalia Snejko
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：April 30, 2007
- 年：2007
- 卷：46
- 期：9
- 页码：3475 - 3484
- 全文大小：467K
- 年卷期：v.46,no.9(April 30, 2007)
- ISSN：1520-510X
文摘
Eight 2D and 3D metal-organic framework (MOF) rare earth naphthalenedisulfonates have been obtained. Thedifferent geometry of the naphthalenedisulfonic acids used as connectors [(1,5-NDS) and (2,6-NDS)] gives rise tothe three new structure types. In Ln(OH)(1,5-NDS)H2O, LnPF-1 (lanthanide polymeric framework; Ln = La, Nd, Pr,Sm and Eu), the lanthanide ion is octacoordinated. Its 3D structure is formed by (Ln2O14)-S-(Ln2O14) infinitechains, connected through complete NDS connectors. LnPF-2 (Ln = Nd), with the same empirical formula as theformer, and the lanthanide in octa- and nonacoordination, owns an arrangement of sulfonate bridges and neodymiumpolyhedra that gives rise to a 2D structure. [Ln5(2,6-NDS)3(OH)9(H2O)4](H2O)2, LnPF-3 (Ln = Nd, Eu), demonstratesthat it is possible to obtain a 3D structure with (2,6-NDS), when a greater Ln/connector ratio is employed. It isworth pointing out the existence, in this latter family of compounds, of a 
5-OH group, whose hydrogen atom isvery close to one-sixth Ln atom (distance Ln···H = 2.09 Å). The materials, with high thermal stability, act as activeand selective bifunctional heterogeneous catalysts in oxidation of linalool yielding cyclic hydroxy ethers. The absenceof any 3D Nd-Nd magnetic interaction is explained due to the inner nature of 4f orbitals of Nd3+, which do notfavor the magnetic exchange. The influence of the polymeric frame matrix results in a better photoluminescenceefficiency for NdPF-1.
5-OH group, whose hydrogen atom isvery close to one-sixth Ln atom (distance Ln···H = 2.09 Å). The materials, with high thermal stability, act as activeand selective bifunctional heterogeneous catalysts in oxidation of linalool yielding cyclic hydroxy ethers. The absenceof any 3D Nd-Nd magnetic interaction is explained due to the inner nature of 4f orbitals of Nd3+, which do notfavor the magnetic exchange. The influence of the polymeric frame matrix results in a better photoluminescenceefficiency for NdPF-1.