Pillaring of CdCl2-like layers in lanthanide metal-organic frameworks:: Synthesis, structure, and photophysical properties
Pillaring of CdCl2-like layers in lanthanide metal-organic frameworks:: Synthesis, structure, and photophysical properties
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DOI：
10.1002/chem.200800240
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发表时间：
2008-01-01
影响因子：
4.3
通讯作者：
Natarajan, Srinivasan
中科院分区：
文献类型：
--
作者：
Mahata, Partha;Ramya, K. V.;Natarajan, Srinivasan
通过镧系元素、吡啶-2，3-二甲酸、苯-1，4-二甲酸和水的水热反应，合成了一系列新的镧系元素三维混合羧酸盐，其通式为[M-2（H2O）（4）][{C5 H3 N（COO）（2）}（2）{C6 H4-（COO）（2）}] M=La（I），Pr（II），Nd（III）.该结构由M2 O 14 N2二聚体单元通过吡啶-2，3-二羧酸酯部分连接以形成由对苯二甲酸酯单元柱撑的二维层组成。ne结构还具有两个配位的水分子，其排列形成一维螺旋链，并且可以被可逆地吸附。层内的连通性非常类似于具有3（6）拓扑的CdCl 2层状结构。据我们所知，这是第一次在镧系金属有机骨架化合物中观察到CdCl 2拓扑结构。Eu ~（3+）和Tb ~（3+）（2%和4%）部分取代La ~（3+），产生红色/粉红色或绿色特征发光，表明是配体敏化的金属中心发光。Nd化合物III通过上转换过程显示出有趣的紫外和蓝光发射。
A hydrothermal reaction of lanthanide salts, pyridine-2,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, and water gave rise to a new series of three-dimensional mixed carboxylates (homocyclic and heterocyclic) of lanthanides with the general formula [M-2(H2O)(4)][{C5H3N(COO)(2)}(2){C6H4-(COO)(2)}] M=La (I), Pr (II), and Nd (III). The structure consists of M2O14N2 dimeric units connected by pyridine-2,3-dicarboxylate moieties to form two-dimensional layers that are pillared by terephthalate units. ne structures also possess two coordinated water molecules, which are arranged to form one-dimensional helical chains and can be reversibly adsorbed. The connectivity within the layers closely resembles that of the CdCl2 layered structure with 3(6) topology. To the best of our knowledge, this is the first observation of CdCl2 topology in lanthanide metal-organic framework compounds. Partial substitution of La3+ in I by Eu3+ and Tb3+ (2 and 4%) gives rise to characteristic red/pink or green emission, which suggests a ligand-sensitized metal-centered emission. The Nd compound III shows interesting UV and blue emission through an up-conversion process.