Apical Ligand Substitution, Shape Recognition, Vapor-Adsorption Phenomenon, and Microcalorimetry for a Pillared Bilayer Porous Framework That Shrinks or Expands in Crystal-to-Crystal Manners upon Change in the Cobalt(II) Coordination Environment

作者：Zeng, Ming Hua^*; Hu, Sheng; Chen, Qing; Xie, Gang; Shuai, Qi; Gao, Sheng Li; Tang, Li Yuan

来源：Inorganic Chemistry, 2009, 48(15): 7070-7079.

DOI：10.1021/ic801794e

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.

• 出版日期2009-8-3
• 单位广东工业大学; 广西师范大学; 西北大学