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3.1.2 Hexahedra (cubes). MOPs exhibit several examples of structures which can be regarded as cubes. Indeed, several authors have chosen to adopt the nomenclature metal–organic cubes (MOC), however such terminology can be ambiguous since it does not necessarily address the fine details of the MOP and its constituent parts. Nevertheless, such MOPs are capable of serving as SBBs such as those first reported by Eddaoudi and co-workers in 2004.155 This cube is constructed from Ni2+ ions and 4,5-imidazoledicarboxylic acid (Fig. 9), is anionic and has the formula [Ni8L12]20 (H3L=4,5-imidazoledicarboxylic acid). The 8 Ni2+ ions reside at the vertices of a cube and are linked through 12 L ligands which coordinate in a bis-chelating fashion. These cubes were subsequently investigated by other research groups and incorporated into framework MOMs. In 2005, Xu and co-workers reported the assembly of these cubes into a framework via bridging with Na+ cations ([2], Table 1).184 In Xu’s structure, the authors report that the ligand is fully deprotonated (in contrast with the structure reported by Eddaoudi) due to the use of a strong base, sodium hydroxide. Two types of cavity were observed: the cavity of the cube itself; a cavity generated by the linking of the cubes into a 3-periodic array. The distance from the center of the cube to the closest non-hydrogen atom of the imidazole ring is 3.236 A ˚ and the inner cavity of the cube exhibits a volume of |
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2楼2011-09-06 08:56:26
