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