Mechanochemistry, an Easy Technique to Boost the Synthesis of CuI Pyrazine Coordination Polymers,Crystal Growth & Design |
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Mechanochemistry, an Easy Technique to Boost the Synthesis of CuI Pyrazine Coordination Polymers,Crystal Growth & Design
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Depending on the experimental conditions, the solid-state reactions of CuI with pyrazine (pyz) yield three distinct coordination polymers (CPs): a double chain polymer [Cu2I2(pyz)]n (yellow powder) and a single strand [CuI(pyz)]n (red powder) and its new isomeric compound [(CuI)2(pyz)2]n (orange powder), which present dimers of CuI bridged by the pyrazine ligands. The conversions among the three CPs were studied: by heating to 110 °C, [CuI(pyz)]n or [(CuI)2(pyz)2]n convert into [Cu2I2(pyz)]n, which reverts to the starting compounds upon kneading or grinding in the presence of pyrazine. The orange isomer [(CuI)2(pyz)2]n is obtained only when the solid-state reaction is performed with neat grinding or by direct melting of the pyrazine; it is unstable in the presence of solvent or vapor, and it readily transforms into the red isomer. The structure of [(CuI)2(pyz)2]n was determined by X-ray powder diffraction. [Cu2I2(pyz)]n reacts also with 4-cyanopyrazine to yield the mixed ligand compound [(CuI)(4CN-py)2 py]n, which, when heated, decomposes into [Cu2I2(pyz)]n and [(CuI)4(4CN-py)5]n.
中文翻译：
根据实验条件，CuI与吡嗪（pyz）的固态反应会生成三种不同的配位聚合物（CPs）：双链聚合物[Cu 2 I 2（pyz）] n（黄色粉末）和单链[ CuI（pyz）] n（红色粉末）及其新的异构化合物[（CuI）2（pyz）2 ] n（橙色粉末），它们呈现由吡嗪配体桥接的CuI二聚体。研究了三个CP之间的转化率：加热至110°C，[CuI（pyz）] n或[（CuI）2（pyz）2 ] n转化为[Cu 2 I 2（pyz）] n在吡嗪存在下进行捏合或研磨后，还原为起始化合物。橙色异构体[（CuI）2（pyz）2 ] n仅在通过纯磨或吡嗪直接熔融进行固相反应时得到。在溶剂或蒸气存在下不稳定，并且容易转化为红色异构体。通过X射线粉末衍射确定[（CuI）2（pyz）2 ] n的结构。[Cu 2 I 2（pyz）] n也与4-氰基吡嗪反应生成混合配体化合物[（CuI）（4CN-py）2 py] n，在加热时分解为[Cu 2 I 2（pyz）] n和[（CuI）4（4CN-py）5 ] n。 |
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