Anion-directed self-assembly of lanthanide-notp compounds and their fluorescence, magnetic, and catalytic properties
Anion-directed self-assembly of lanthanide-notp compounds and their fluorescence, magnetic, and catalytic properties
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镧系元素-notp化合物的阴离子定向自组装及其荧光、磁性和催化性能
DOI：
10.1002/chem.200601097
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Zheng, Li-Min
中科院分区：
文献类型：
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作者：
Bao, Song-Song;Ma, Li-Fang;Zheng, Li-Min
1,4,7-三氮杂环壬烷-1,4,7-三基-三（亚甲基膦酸）[notpH(6), C9H18N3-(PO3H2)(3)]与不同镧系盐反应可得到四种类型的Ln-notp化合物：(Ln {C9H20N3 (PO3H)(2) -(警察丙)}(3号)(H2O)]中心点4水(1),(Ln =欧盟欧盟(1),Gd (1 Gd)结核病(M)], [Ln - {C9H20N3 (PO3H)(2)(警察丙)}(H2O)] Cl中心点3 h O (2) (2) (Ln =欧盟欧盟(2),Gd (2 Gd),结核(M)] [Ln {C9H20N3 (PO3H)(2)(警察丙)}- (H2O)] ClO4中心点8 h(2)啊,(3)(Ln =欧盟欧盟(3),Gd Gd)(3),和(Ln {C9H20N3 - (PO3H)(2)(警察丙)}H2O)] ClO4中心点3 h (2) O (4), (Ln = Gd (4 Gd),结核病结核病(4)]。每种类型中的化合物都是同构的。在化合物1中，发现了{Ln(2)- (notpH(4))(2)(NO3)(2)(H2O)(2)}二聚体，其中两个镧系原子由两对O-P-O和一对mu-O桥连接。NO3-离子作为双齿末端配体。化合物2含有类似的二聚体单位{Ln(2)(notpH(4))(2)(H2O)(2)}，它们通过一对O-P-O桥进一步连接成一个交替链。Cl-离子参与了链间氢键网络。在化合物3中也发现了类似的链状结构；然而，在这种情况下，这些链是由ClO4-反离子通过氢键相互作用连接起来的，在（011）平面上形成了一个波动层。这些层通过氢键相互作用融合，形成三维超(m)分子网络，在[100]方向上具有大通道。化合物4显示出一个有趣的砖墙状层结构，其中相邻的镧系原子通过一对O-P-O桥连接。ClO4-反离子和晶格水分子在两层之间。在所有化合物中，三氮杂环氮原子不与Ln（III）离子配位。阴离子和pH值被认为在指导特定结构的形成中起着关键作用。研究了Eu和Tb化合物的荧光光谱性质、Gd化合物的磁性能以及4Gd的催化性能。
Reactions of 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylene- phosphonic acid) [notpH(6), C9H18N3-(PO3H2)(3)] with different lanthanide salts result in four types of Ln-notp compounds: [Ln{C9H20N3(PO3H)(2)-(PO3)}(NO3)(H2O)]center dot 4 H2O (1), [Ln = Eu (1Eu), Gd (1Gd), Tb (M)], [Ln-{C9H20N3(PO3H)(2)(PO3)}(H2O)]Cl center dot 3H(2)O (2) [Ln = Eu (2Eu), Gd (2Gd), Tb (M)] [Ln{C9H20N3(PO3H)(2)(PO3)}- (H2O)]ClO4 center dot 8H(2)O, (3) [Ln = Eu (3Eu), Gd (3Gd)], and [Ln{C9H20N3-(PO3H)(2)(PO3)}H2O)]ClO4 center dot 3H(2)O (4), [Ln = Gd (4Gd), Tb (4Tb)]. Compounds within each type are isostructural. In compounds 1, dimers of {Ln(2)- (notpH(4))(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 mu-O bridges. The NO3- ion serves as a bidentate terminal ligand. Compounds 2 contain similar dimeric units of {Ln(2)(notpH(4))(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 supra(m)olecular 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 Ln(III) 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 4Gd were also studied.