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Two copper(i) cyanide coordination polymers modified by semi-rigid bis(benzimidazole) ligands: syntheses, crystal structures, and electrochemical and photocatalytic properties.两种由半刚性双(苯并咪唑)配体修饰的氰化亚铜(I)配位聚合物:合成、晶体结构以及电化学和光催化性能
Dalton Trans. 2016 Nov 1;45(43):17474-17484. doi: 10.1039/c6dt03270b.
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Electrical Conductivity and Strong Luminescence in Copper Iodide Double Chains with Isonicotinato Derivatives.含异烟酸酯衍生物的碘化亚铜双链中的电导率和强发光特性
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基于由2-氨基吡嗪连接的Cu I链的配位聚合物的多刺激响应微层和纳米层

Multistimuli Response Micro- and Nanolayers of a Coordination Polymer Based on Cu I Chains Linked by 2-Aminopyrazine.

作者信息

Conesa-Egea J, Gallardo-Martínez J, Delgado S, Martínez J I, Gonzalez-Platas J, Fernández-Moreira V, Rodríguez-Mendoza U R, Ocón P, Zamora F, Amo-Ochoa P

机构信息

Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Madrid, 28049, Spain.

Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Madrid, 28049, Spain.

出版信息

Small. 2017 Sep;13(33). doi: 10.1002/smll.201700965. Epub 2017 Jul 10.

DOI:10.1002/smll.201700965
PMID:28692791
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5687565/
Abstract

A nonporous laminar coordination polymer of formula [Cu I (2-aminopyrazine)] is prepared by direct reaction between CuI and 2-aminopyrazine, two industrially available building blocks. The fine tuning of the reaction conditions allows obtaining [Cu I (2-aminopyrazine)] in micrometric and nanometric sizes with same structure and composition. Interestingly, both materials show similar reversible thermo- and pressure-luminescent response as well as reversible electrical response to volatile organic solvents such as acetic acid. X-ray diffraction studies under different conditions, temperatures and pressures, in combination with theoretical calculations allow rationalizing the physical properties of this compound and its changes under physical stimuli. Thus, the emission dramatically increases when lowering the temperature, while an enhancement of the pressure produces a decrease in the emission intensity. These observations emerge as a direct consequence of the high structural flexibility of the Cu I chains which undergo a contraction in CuCu distances as far as temperature decreases or pressure increases. However, the strong structural changes observed under high pressure lead to an unexpected effect that produces a less effective CuCu orbital overlapping that justifies the decrease in the intensity emission. This work shows the high potential of materials based on Cu I chains for new applications.

摘要

通过工业上可得的两种原料碘化亚铜(CuI)和2 - 氨基吡嗪直接反应,制备出了化学式为[CuI(2 - 氨基吡嗪)]的无孔层状配位聚合物。对反应条件进行微调,可以得到具有相同结构和组成的微米级和纳米级尺寸的[CuI(2 - 氨基吡嗪)]。有趣的是,这两种材料都表现出相似的可逆热发光和压力发光响应,以及对挥发性有机溶剂(如乙酸)的可逆电响应。在不同条件、温度和压力下进行的X射线衍射研究,结合理论计算,有助于阐明该化合物的物理性质及其在物理刺激下的变化。因此,降低温度时发射显著增加,而压力增大则导致发射强度降低。这些观察结果是CuI链具有高结构灵活性的直接结果,随着温度降低或压力增加,CuCu距离会收缩。然而,在高压下观察到的强烈结构变化导致了意想不到的效果,即CuCu轨道重叠效率降低,这解释了发射强度的下降。这项工作展示了基于CuI链的材料在新应用方面的巨大潜力。

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