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室温下,在醇水溶液中合成了2个新型配合物,[Zn(phen)3]2·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(C10H18O4=癸二酸)(1)和[Co(phen)3]2·[Co(H2O)6]·(C10H16O4)3·30H2O(2),并对配合物进行了元素分析分析、红外光谱分析、热重分析以及晶体结构研究.配合物(1)的基本结构单元中含有一个电中性配位单元[Zn(C10H16O4)·(H2O)3]、二个配位阳离子[Zn(phen)3]2+、二个游离的癸二酸根和20个晶格水.Zn原子有两种配位模式,在[Zn(phen)3]2+配位单元中Zn原子与三个邻菲啰啉的六个N原子配位,构成略有畸变的八面体,Zn原子位于八面体的对称中心;在[Zn(C10H16O4)·(H2O)3]配位单元中Zn原子采取五配位的三角双锥构型,两个羧基均采取单齿配位,同一个癸二酸根与相邻的不同Zn原子配位,将相邻的[Zn(C10H16O4)·(H2O)3]配位单元连接起来,自组装得到了无限链状结构.配合物以癸二酸根为模板在ab平面形成了有序水层,该水层由5元,6元水簇,以及其他由羧基参与的各元环组成.与一般常见的6元水簇不同,配合物1中的6元水簇采取了高能量的类似苯环的平面构象.配合物(2)的基本结构单元中含有一个[Co(H2O)6]2+配位阳离子、二个[Co(phen)3]2+配位阳离子、三个游离的癸二酸根和30个晶格水.Co原子也有两种配位模式.在[Co(phen)3]2+配位单元中,Co原子与三个邻菲啰啉的六个N原子配位,构成略有畸变的八面体,Co原子位于八面体的对称中心.在[Co(H2O)6]2+配位单元中Co(II)与6个配位水的氧原子配位,6个配位水中的6个原子和Co(Ⅱ)形成八面体结构.通过水分子之间及水分子和羧基阴离子间的氢键形成了二维有序水层,二维水层中最小的构筑基元为6元环的水,最大的构筑基元为16元环水,每个水环中分别含有6个和16个游离的没有配位的水分子,水分子之间通过很强的氢键作用形成环形的超分子水簇.这些基元片断在二维空间扩展开来,形成二维有序水层.有趣的是,在该水层上通过水分子之间的分子间氢键形成了16元大环水簇,它与两端的六元环共用六条边,每一个16元水环中含有16个游离的没有配位的水分子,水分子之间通过氢键作用形成环形超分子水簇,每个水分子同时作为氢键的给体和受体.[Co(H2O)6]2+和四个羧酸根离子位于十六元环水的中心,与其周围的游离水分子形成了十二个氢键,同时与环外的游离水和羧酸根形成了十个氢键,对大环水聚集体起到稳定作用.
At room temperature, two new complexes were synthesized in aqueous alcohol solution. The complex of [Zn (phen) 3] 2 · [Zn (C10H16O4) · (H2O) 3] · (C10H16O4) 2 · 20H2O (C10H18O4 = sebacic acid) 1) and [Co (phen) 3] 2 · [Co (H2O) 6] · (C10H16O4) 3 · 30H2O (2) were synthesized and characterized by elemental analysis, IR, TG and crystal structure The basic structural unit of complex (1) contains one electroneutral coordination unit [Zn (C10H16O4) · (H2O) 3], two coordination cations [Zn (phen) Sebacate and 20 lattice water. There are two kinds of coordination modes for Zn atom, in which the Zn atom coordinates with the six N atoms of the three phenanthrolines in the [Zn (phen) 3] 2+ coordination unit , Constituting a slightly distorted octahedron, the Zn atom is located at the center of symmetry of the octahedron; the Zn atom in the [Zn (C10H16O4) · (H2O) 3] coordination unit adopts a five-coordinate triangular double cone configuration, All take the monodentate coordination. The same sebacate is coordinated with the adjacent Zn atoms, and the adjacent [Zn (C10H16O4) · (H2O) 3] coordination units are connected to form an infinite chain Structure. The complex sebacate as a template in the ab plane to form an ordered water layer, the water layer from 5 yuan , 6-membered water cluster, and other elements involved in the carboxyl group.Compared with the common 6-membered water cluster, the 6-membered water cluster in complex 1 adopts a high energy benzene-like planar conformation (2) contains one [Co (H 2 O) 6] 2+ coordination cation, two [Co (phen) 3] 2+ coordination cations, three free sebacates and 30 lattices There are also two kinds of coordination modes in water and Co atoms. In [Co (phen) 3] 2+ coordination units, the Co atoms coordinate with the six N atoms of the three phenanthrolines to form a slightly distorted octahedron , The Co atom is located at the symmetry center of the octahedron. Co (II) coordinates with the oxygen atoms of 6 coordination water in the [Co (H2O) 6] 2+ coordination unit, and 6 atoms in 6 coordination water and Co (Ⅱ) forms an octahedron structure, and a two-dimensional ordered water layer is formed by hydrogen bonding between water molecules and water molecules and carboxyl anions. The smallest building block in the two-dimensional water layer is 6-membered ring water, The largest building block is 16 yuan of circular water, each water ring contains 6 and 16 free uncoordinated water molecules, the water molecules form a ring of supramolecular water clusters through strong hydrogen bonds These primitives are in two dimensions Space expands to form a two-dimensional, ordered water layer Interestingly, a 16-membered macrocyclic water cluster is formed on this water layer by intermolecular hydrogen bonding between water molecules, sharing six six-membered rings on both ends Side, each 16 yuan water ring contains 16 free uncoordinated water molecules, water molecules formed by hydrogen bonding between the ring-shaped supramolecular water clusters, each water molecule at the same time as a hydrogen bond donor and acceptor . [Co (H2O) 6] 2+ and four carboxylate ions are located in the center of a sixteen-membered ring water, forming twelve hydrogen bonds with the free water molecules around it and simultaneously forming with free water and carboxylate groups outside the ring Ten hydrogen bonds, the water ring aggregates play a stabilizing role.