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 shu

Distinguishable Polymorphs in Color: Cyano-Bridged Heterometallic Pentagonal Ribbons via Cuprophilic Aggregation

1.
1. School of Chemistry & Material Science, Key Laboratory of Magnetic Molecules and Magnetic Information Material, Ministry of Education, Shanxi Normal University, Linfen, Shanxi 041004, China;
2.
2. Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, China

Corresponding author: ZHANG Xian-Ming,
Received Date: 20 April 2015
Available Online: 5 June 2015
Fund Project: 国家重点基础研究发展计划(973项目2012CB821701) (973项目2012CB821701)中国教育部项目(No.IRT1156) (No.IRT1156)国家杰出青年科学基金(No.20925101) (No.20925101)运城学院青年教师科研启动项目(No.YQ-2013013)资助。 (No.YQ-2013013)

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.
- cuprophilicity;polymorph;heterometa;pentagon;aggregate
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