The reaction of Ni(mnt)₂ (mnt = 1,2-dicyano-1,2-ethylenedithiolate) with CuI in THF results in the formation of a Ni(mnt)₂Cu₄I₄ unit with an eight-membered Cu₄I₄ crown motif. Coordination polymers with Ni(mnt)₂Cu₄I₄ building units, having doubly bridged 1-D chains, were formed with bulky NBu₄ counterions. To pack the bulky NBu₄ cations into the crystal structure, no direct interactions between the 1-D chain structures are observed. When the bulky NBu₄ cations are exchanged for small sodium cations, direct interactions between the 1-D chain structures dominate. A doubly bridged 2-D sheet structure is formed through the bridging of the cyano groups of the Ni(mnt)₂Cu₄I₄ units of neighboring 1-D chain structures by sodium atoms. The monomeric [Na₂(18-crown-16)]₂[Ni(mnt)₂Cu₄I₄] complex is formed when the sodium cations of the 2-D sheet structure are captured by 18-crown-6. The configuration of the coordination polymer or the monomer is controlled through the selection of the appropriate countercation to the Ni(mnt)₂Cu₄I₄ building unit. Furthermore, the eight-membered Cu₄I₄ crown motifs in the 2-D sheet structure captures sodium cations. In this regard, we propose that the flexible Cu₄I₄ crown motif is capable of capturing atoms or molecules of various sizes; such a material may act as a useful molecular adsorbent through electrostatic interactions.

中文翻译：

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二维片状配位聚合物和包含八元Cu ₄ I ₄冠状图案的单体的可控自组装

Ni（mnt）₂（mnt = 1,2-二氰基-1,2-亚乙基二硫代硫酸盐）与CuI在THF中的反应导致形成带有八元Cu ₄的Ni（mnt）₂ Cu ₄ I ₄单元。我₄冠图案。与Ni（mnt）₂ Cu ₄ I ₄结构单元具有双桥式1-D链的配位聚合物与庞大的NBu ₄抗衡离子形成。要将庞大的NBu ₄阳离子堆积到晶体结构中，没有观察到1-D链结构之间的直接相互作用。当笨重的NBu ₄阳离子交换成小的钠阳离子，一维链结构之间的直接相互作用占主导。通过钠原子桥接相邻的1-D链结构的Ni（mnt）₂ Cu ₄ I ₄单元的氰基，形成双桥2-D片状结构。当2-D片状结构的钠阳离子被18-冠-6捕获时，形成单体[Na ₂（18-冠-16）] ₂ [Ni（mnt）₂ Cu ₄ I ₄ ]络合物。通过选择对Ni（mnt）₂ Cu ₄ I的适当抗衡阳离子，可以控制配位聚合物或单体的构型_4个建筑单元。此外，二维薄片结构中的八元Cu ₄ I ₄冠状图案捕获了钠阳离子。在这一点上，我们提出柔性的Cu ₄ I ₄冠基序能够捕获各种大小的原子或分子。这样的材料可以通过静电相互作用充当有用的分子吸附剂。