SIZE TUNED FRAMEWORK DIMENSIONALITY

Structural Diversity and Luminescent Properties of Lanthanide 2,2- and 2,3-dimethylsuccinate frameworks
P J Saines, M Steinmann, J-C Tan, H H-M Yeung and A K Cheetham
CrystEngComm 15, 100-110 (2013)

The structures of fourteen new lanthanide frameworks (La, Ce, Eu, Tb, Y and Lu) containing the 2,2- or 2,3-dimethylsuccinate ligands are reported. While the majority of the known 2,2-dimethylsuccinate frameworks feature two dimensionally bonded layers, capped by hydrophobic methyl groups, several of these new frameworks adopt quite different architectures. These include one dimensional inorganically connected chains (La and Ce) with only non-covalent interactions in the other two dimensions, and three dimensional covalently bonded frameworks (Eu and Lu) with spaces in their structure to accommodate the bulky methyl groups. The new 2,3-dimethylsuccinate frameworks (La and Y) adopt three-dimensional covalently bonded frameworks. The factors affecting the formation of structures with different dimensionalities are examined and compared to previously reported transition metal frameworks. In addition, the sequence of phases formed with changing lanthanide size, concentrations and temperatures are rationalised. The luminescent properties of several 1- and 2-D frameworks doped with Eu and Tb are reported, with the Y host exhibiting the most intense emission.

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