含有十核羧酸-水杂化簇合物的二维铜配位聚合物的构筑

A hybrid carboxylate-water decamer with a discrete octameric water moiety self-assembled in a 2D copper(Ⅱ) coordination polymer

以新生的氢氧化铜、2,2'-二苯基二羧酸(H2bpda)以及柔性配体1,3-二(4-吡啶)丙烷(bpp)为原料,超声反应条件下,在甲醇-水混合溶剂中合成了1个新型配合物,{[Cu2(bpp)2(H2O)2(bpda)2]·6H2O}n(1),并对该配合物进行了元素分析、红外光谱分析、热重分析、脱水/重新吸水分析以及晶体结构研究.X射线单晶结构分析表明,配合物1中含有一种由类似椅式构象的六核水簇及两个水分子所组成的八核水簇.该八核水簇结构类似环脂烃(1r,4r)二甲基-环己烷,显示出水分子簇与有机分子结构上的相似性.有趣的是,该八核水簇与周围羧酸根中的氧原子通过氢键作用形成了类似于(H2O)10纯水簇的十核羧酸-水杂化簇合物.此外,该配合物具有可逆的脱水/重新吸水性能.

An octameric water moiety which consists of a chairlike water hexamer and two pendent water molecules in the 1,4-diaxial positions and shows a similar structure to the hydrocarbon （lr,4r）-l,4-dimethylcyclohexane, is unambiguously trapped in a 2D Cu（II） mixed-ligand coordination polymer, {[Cuz（bpp）z（HzO）z（bpda）2]＇6HzO}n （1） （bpp = 1,3-bis（4-pyridyl）propane and H2bpda = 2,2＇-biphenyldicarboxylic acid）. The water octamer can be extended into a hybrid carboxylate-water detainer when carboxylic oxygen atoms from bpda5 are involved. Interestingly, the present hybrid decamer bears a similar structural topology to a butterfly （H20）10 cluster. The reversible dehydration/hydration of 1 is determined by X-ray powder diffraction studies.