期刊
INORGANIC CHEMISTRY
卷 48, 期 15, 页码 7070-7079出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic801794e
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资金
- NSFC [20561001]
- S FGX [0832001Z]
- Ministry of Education China [NCET-07-217]
- New Century of Guangxi [2006201]
- GKN [0630006-5D]
A 2D pillared bilayer coordination polymer, [Co(5-NH2-bdc)(bpy)(0.5)(H2O)]center dot 2H(2)O (1; 5-NH2-bdc = 5-aminoisophthalate; bpy = 4,4'-bipyridine) has been hydrothermally synthesized and shows a novel microporous host framework with 1 D channels and high thermal stability (similar to 400 degrees C). The framework of 1 exhibits reversible single-crystal-to-single-crystal transformations upon removing and rebinding the coordinated waters as well as replacing them with MeOH and EtOH from the solvent. X-ray crystallography reveals that the coordination geometry of Co(II) changes from octahedron to square pyramid, as well as the shrinkage/expansion of pore deformation in respect to the subsequent shear motion of bpy pillars and vice versa. The dehydrated form 2 exhibits a shape recognition ability, which can accommodate linear molecules, such as MeCN and 2-propynyl alcohol, and interesting storage capabilities for oversized MeOH, EtOH, and benzene molecules, concomitant with spongelike dynamic transformation. The microcalorimetric study indicates that the crystalline state-liquid guest exchange and guest inclusion processes (1 superset of D MeOH or EtOH, 2 superset of MeOH, EtOH or MeCN) are feasibly endothermic reactions with the values of molar enthalpy, Delta H-m(theta) of +21.38(96), +12.68(85), +25.92(86), +17.03(57), and +14.93(75) kJ mol(-1), respectively.
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