Inorganic-organic hybrid materials are of continuing interest, because they may possess not only the intriguing properties of inorganic components but also the structure flexibility of organic materials. Compared with the inorganic-organic hybrid materials based on single metal ions as nodes, those based on high-nuclearity metal clusters are better at maintaining specific geometries and imparting physical properties to hybrids through the assembly process. On the other hand, low-dimensional metal oxohalides are attractive due to their pleasing structures and specific properties such as magnetic frustration and anisotropic conductivity.
The research group headed by Prof. HUANG Xiaoying at Fujian Institute of Research on the Structure of Matter(FJIRSM), Chinese Academy of Sciences(CAS), has made significant progress on the design and synthesis of inorganic-organic hybrid compounds based on heterometallic oxohalide nanoclusters.
They successfully prepared the first lanthanide antimony oxohalide compound featuring a nanometer-sized cluster [Pr4Sb12O18Cl17]5- with nearly perfect Td-symmetry by using a synergistic ‘structure scissor’ strategy, in which both the lone pairs and halide ions play important roles in constructing the discrete structure. Furthermore, by substituting partially the Cl- supporting ligands with dicarboxylate ligands with angular or linear geometry as linkers, the hybrids with one-dimensional chain-like (2-MepyH)4[Pr4Sb12O18Cl14(1,3-bdc)] and two-dimensional wave-like (2-MepyH)3[Pr4Sb12O18Cl11(1,4-bdc)2]·4.5H2O structures based on the novel oxohalide nanoclusters as nodes have been realized, indicating that the nanocluster is an excellent structural building unit for constructing inorganic-organic hybrid materials (Angew. Chem. Int. Ed. 2011, 50, 8110–8113.).
This research provides a new route towards the rational design of diversiform inorganic-organic hybrid structures based on the high-nuclearity cluster SBUs by introducing diverse ligands.
(Novel lanthanide antimony oxohalide nanocluster and inorganic-organic hybrid network based on the nanocluster)
