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一种罕见的双 T5(2) 水带被困在银(I)配位聚合物主体中:溶剂对反式环己烷二羧酸根和 4,4'-联吡啶与银(I)链的组装及其发光性能的影响。

An unusual double T5(2) water tape trapped in silver(I) coordination polymer hosts: influence of the solvent on the assembly of Ag(I)-4,4'-bipyridine chains with trans-cyclohexanedicarboxylate and their luminescent properties.

机构信息

College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002, P. R. China.

出版信息

Dalton Trans. 2012 Nov 7;41(41):12872-81. doi: 10.1039/c2dt31847d.

DOI:10.1039/c2dt31847d
PMID:22986411
Abstract

In this paper, four silver(I) compounds, namely, {[Ag(4)(bipy)(4)(chda)]·2NO(3)·10H(2)O}(n) (1), {[Ag(2)(bipy)(2)(chda)]·14H(2)O}(n) (2), {[Ag(2)(bipy)(2)(chda)]·3EG·2H(2)O}(n) (3) and {[Ag(2)(bipy)(2)(chda)]·H(2)chda}(n) (4) (where bipy = 4,4'-bipyridine, H(2)chda = trans-cyclohexane-dicarboxylate and EG = ethylene glycol), have been synthesized and characterized by single-crystal X-ray diffraction analyses. In all of these compounds, the Ag(I) centers are linked by bipy ligands to form 1D Ag(I)-bipy chain structures. The chda(2-) anions of compound 1 adopt a μ(4)-coordination mode to connect the Ag(I)-bipy chains, forming a H-beam-like chain. In 2, the chda(2-) anions adopt a μ(2)-coordination mode to connect the Ag(I)-bipy chains resulting in two distinct 2D brick wall-like layers. These layers are further stacked in an ···ABAB··· fashion through interlayer π···π stacking interactions giving rise to a 3D framework consisting of quasi-rectangular channels, in which an unusual double T5(2) water tape is trapped. For 3 and 4, the chda(2-) anions show a similar μ(4)-coordination mode to that of 1 and connect the Ag(I)-bipy chains to form 2D grid layers with identical compositions and connective topologies. The experimental studies show that the final structures are greatly influenced by the molar ratio of the components and the solvents, which can be rationally interpreted by the existence of various supramolecular interactions between the host and guest molecules within these compounds through a systematic structural comparison. Additionally, the thermal stability and luminescent properties of these compounds were also studied.

摘要

本文合成并通过单晶 X 射线衍射分析了四种银(I)化合物,分别为:{[Ag(4)(bipy)(4)(chda)]·2NO(3)·10H(2)O}(n) (1)、{[Ag(2)(bipy)(2)(chda)]·14H(2)O}(n) (2)、{[Ag(2)(bipy)(2)(chda)]·3EG·2H(2)O}(n) (3) 和 {[Ag(2)(bipy)(2)(chda)]·H(2)chda}(n) (4)(其中 bipy = 4,4'-联吡啶,H(2)chda = 反式环己烷二羧酸和 EG = 乙二醇)。在所有这些化合物中,Ag(I) 中心通过 bipy 配体连接形成 1D Ag(I)-bipy 链结构。化合物 1 中的 chda(2-)阴离子采用 μ(4)-配位模式连接 Ag(I)-bipy 链,形成 H 梁状链。在 2 中,chda(2-)阴离子采用 μ(2)-配位模式连接 Ag(I)-bipy 链,导致形成两个不同的 2D 砖状层。这些层通过层间 π···π 堆积相互作用以···ABAB···方式进一步堆积,形成由准矩形通道组成的 3D 骨架,其中捕获了一种不寻常的双 T5(2)水带。对于 3 和 4,chda(2-)阴离子表现出与 1 相似的 μ(4)-配位模式,连接 Ag(I)-bipy 链形成具有相同组成和连接拓扑的 2D 网格层。实验研究表明,最终结构受反应物摩尔比和溶剂的极大影响,通过对这些化合物中主体和客体分子之间各种超分子相互作用的系统结构比较,可以合理地解释这种影响。此外,还研究了这些化合物的热稳定性和发光性质。

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