| 颜色可区分的氰桥五边形带经亲铜作用聚集的异金属多形体 | |
| Distinguishable Polymorphs in Color: Cyano-Bridged Heterometallic Pentagonal Ribbons via Cuprophilic Aggregation | |
| 摘要: 水热条件下,环境友好的K2[Ni(CN)4]能缓慢水解形成cis-[Ni(CN)2(H2O)4]单元和氰基配体,并进一步与金属铜(Ⅰ)原子组装形成异金属的五边形带。这些五边形带通过亲铜聚集作用形成二维有色的超分子多形体[(CuCN)2Ni(CN)2(H2O)4](1和2)。研究发现,低温条件下形成了密集态的深蓝色的化合物1,然而高温反应条件形成疏松态的紫色化合物2,这一现象与高温高压的反应条件形成密集态的物质这一规律相违背。结构的进一步分析发现五边形环尺寸的微小改变和二维超分子层间距离的差异是引起这一反常的原因。除此之外,这两个新的化合物也是少见的由亲铜性聚集作用诱导的着色异常的多形体的例子,显示了从深蓝色到紫色的颜色改变。磁性研究证实了平面正方形的[Ni(CN)4]2-中的金属镍(Ⅱ)转换成了有着基态自旋S=1的八面体配位几何中心。 | |
| 关键词: 亲铜作用 多形体 异金属 五边形 聚集 | |
| 基金项目: 国家重点基础研究发展计划(973项目2012CB821701),中国教育部项目(No.IRT1156),国家杰出青年科学基金(No.20925101),运城学院青年教师科研启动项目(No.YQ-2013013)资助。 | |
| Abstract: 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. | |
| Keywords: cuprophilicity polymorph heterometa pentagon aggregate | |
| 投稿时间：2015-04-20 修订日期：2015-06-05 | |
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| 秦英恋,李士利,姜宁,张献明.颜色可区分的氰桥五边形带经亲铜作用聚集的异金属多形体[J].无机化学学报,2015,31(9):1785-1797. | |
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