Details

Autor(en) / Beteiligte

• Bao, Song-Song
• Ma, Li-Fang
• Wang, Yin
• Fang, Ling
• Zhu, Cheng-Jian
• Li, Yi-Zhi
• Zheng, Li-Min

Titel

Anion-Directed Self-Assembly of Lanthanide-notp Compounds and Their Fluorescence, Magnetic, and Catalytic Properties

Ist Teil von

• Chemistry : a European journal, 2007-01, Vol.13 (8), p.2333-2343

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2007

Link zum Volltext

Quelle

Wiley Online Library Journals Frontfile Complete

Beschreibungen/Notizen

• Reactions of 1,4,7‐triazacyclononane‐1,4,7‐triyl‐tris(methylenephosphonic acid) [notpH6, C9H18N3(PO3H2)3] with different lanthanide salts result in four types of Ln–notp compounds: [Ln{C9H20N3(PO3H)2(PO3)}(NO3)(H2O)]⋅4 H2O (1), [Ln = Eu (1 Eu), Gd (1 Gd), Tb (1 Tb)], [Ln{C9H20N3(PO3H)2(PO3)}(H2O)]Cl⋅3 H2O (2) [Ln = Eu (2 Eu), Gd (2 Gd), Tb (2 Tb)], [Ln{C9H20N3(PO3H)2(PO3)}(H2O)]ClO4⋅8 H2O, (3) [Ln = Eu (3 Eu), Gd (3 Gd)], and [Ln{C9H20N3(PO3H)2(PO3)}(H2O)]ClO4⋅3 H2O (4), [Ln = Gd (4 Gd), Tb (4 Tb)]. Compounds within each type are isostructural. In compounds 1, dimers of {Ln2(notpH4)2(NO3)2(H2O)2} are found, in which the two lanthanide atoms are connected by two pairs of O‐P‐O and one pair of μ‐O bridges. The NO3− ion serves as a bidentate terminal ligand. Compounds 2 contain similar dimeric units of {Ln2(notpH4)2(H2O)2} that are further connected by a pair of O‐P‐O bridges into an alternating chain. The Cl− ions are involved in the interchain hydrogen‐bonding networks. A similar chain structure is also found in compounds 3; in this case, however, the chains are linked by ClO4− counterions through hydrogen‐bonding interactions, forming an undulating layer in the (011) plane. These layers are fused through hydrogen‐bonding interactions, leading to a three‐dimensional supramolecular network with large channels in the [100] direction. Compounds 4 show an interesting brick‐wall‐like layer structure in which the neighboring lanthanide atoms are connected by a pair of O‐P‐O bridges. The ClO4− counterions and the lattice water molecules are between the layers. In all compounds the triazamacrocyclic nitrogen atoms are not coordinated to the LnIII ions. The anions and the pH are believed to play key roles in directing the formation of a particular structure. The fluorescence spectroscopic properties of the Eu and Tb compounds, magnetic properties of the Gd compounds, and the catalytic properties of 4 Gd were also studied. Dimers, chains, and layers: Reactions of 1,4,7‐triazacyclononane‐1,4,7‐triyl‐tris(methylenephosphonic acid) (notpH6, C9H18N3(PO3H2)3) with different LnX3 lanthanide salts (Ln = Eu, Gd, Tb; X = NO3−, Cl−, ClO4−) result in four types of Ln–notp compounds with layer structures, such as that depicted here. The anions as well as the pH are believed to play key roles in directing the formation of a particular structure. The fluorescence spectroscopic properties of the Eu and Tb compounds, magnetic properties of the Gd compounds, and the catalytic properties of the complex shown are also studied.