Citation: QIN Ying-Lian, LI Shi-Li, JIANG Ning, ZHANG Xian-Ming. Distinguishable Polymorphs in Color: Cyano-Bridged Heterometallic Pentagonal Ribbons via Cuprophilic Aggregation[J]. Chinese Journal of Inorganic Chemistry, ;2015, 31(9): 1785-1797. doi: 10.11862/CJIC.2015.249
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By using environmentally friendly K2[Ni(CN)4] that slowly hydrolyse upon hydrothermal treatment, cis-[Ni(CN)2(H2O)4] units and cyanides were generated and further assembled with Cu(Ⅰ) atoms into pentagonal heterometallic ribbons. Subsequently, these pentagonal ribbons are induced aggregation via cuprophilic interactions into 2D supramolecular coloured polymorphs [(CuCN)2Ni(CN)2(H2O)4] (1 and 2). Dark blue 1 synthesized at a lower temperature is a denser phase while purple 2 synthesized at a higher temperature is a looser phase, which is abnormal to general rule that a higher reaction time and pressure tends to form a denser phase. Careful examination on structures reveals that slight size difference in pentagons and different interlayer distances of 2D supramolecular arrangement contribute to the abnormality. Besides, the titled compounds could be rare cuprophilicity drived examples of coloured polymorphs, which exhibit remarkable colour difference from dark-blue to purple. Magnetic measurements confirmed that diamagnetic Ni(Ⅱ) atom in square planar [Ni(CN)4]2- is transformed into octahedral coordinated Ni(Ⅱ) with ground state spin S=1.
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