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.
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.
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DOI：
10.1021/ic801794e
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发表时间：
2009-07
影响因子：
4.6
通讯作者：
Ming‐Hua Zeng;Sheng Hu;Qing Chen;G. Xie;Q. Shuai;Sheng-li Gao;Li-Yuan Tang
中科院分区：
文献类型：
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作者：
Ming‐Hua Zeng;Sheng Hu;Qing Chen;G. Xie;Q. Shuai;Sheng-li Gao;Li-Yuan Tang
二维柱状双层配位聚合物[Co(5- nh2 -bdc)(bpy)(0.5)(H(2)O)] × 2h (2)O (1); 5- nh2 -bdc = 5-氨基间苯二甲酸酯；bpy = 4,4'-联吡啶)已被水热合成，并显示出具有一维通道和高热稳定性（约400℃）的新型微孔宿主框架。在去除和重新结合配位水以及用溶剂中的MeOH和EtOH取代它们时，1的框架表现出可逆的单晶到单晶的转变。x射线晶体学分析表明，Co（II）的配位几何形态由八面体转变为方金字塔，孔隙变形的收缩/膨胀相对于bpy柱的剪切运动，反之亦然。脱水后的形式2表现出形状识别能力，可以容纳线性分子，如men和2-丙醇，以及超大MeOH， EtOH和苯分子的有趣存储能力，并伴有海绵状的动态转化。微量热研究表明，晶态-液相客体交换和客体包合过程（1个超集MeOH或EtOH， 2个超集MeOH、EtOH或MeCN）是可行的吸热反应，摩尔焓、δ tah (θ)(m)分别为+21.38（96）、+12.68（85）、+25.92（86）、+17.03（57）和+14.93(75)kJ mol（-1）。
A 2D pillared bilayer coordination polymer, [Co(5-NH(2)-bdc)(bpy)(0.5)(H(2)O)] x 2 H(2)O (1; 5-NH(2)-bdc = 5-aminoisophthalate; bpy = 4,4'-bipyridine) has been hydrothermally synthesized and shows a novel microporous host framework with 1D channels and high thermal stability (approximately 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 MeOH or EtOH, 2 superset MeOH, EtOH or MeCN) are feasibly endothermic reactions with the values of molar enthalpy, DeltaH(theta)(m), of +21.38(96), +12.68(85), +25.92(86), +17.03(57), and +14.93(75) kJ mol(-1), respectively.