碱金属阳离子在杂金属聚合物环丙烷-1,1-二羧酸盐构建中的作用

IF 2.6 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

CrystEngComm Pub Date : 2025-03-31 DOI:10.1039/D4CE01319K

Ekaterina N. Zorina-Tikhonova, Anna K. Matiukhina, Alexander A. Korlyukov, Alexander S. Goloveshkin, Konstantin A. Babeshkin, Nikolay N. Efimov, Eugeny V. Alexandrov, Mikhail A. Kiskin and Igor L. Eremenko

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引用次数: 0

摘要

本文合成了具有环丙烷-1,1-二羧酸（H2cpdc）离子的新型NiII配位化合物：{[Na2Ni(cpdc)2(H2O)6]·4H2O}n(1)、{[K6Ni3(cpdc)6(H2O)10]·8H2O}n(2)、{[Rb6Ni3(cpdc)6(H2O)12]·5.5H2O}n(3)和[Cs2Ni(cpdc)2(H2O)8]n(4)。所有配合物均含有单核双螯合物片段{NiII(cpdc)2(H2O)2}2−，由碱原子在一维配位聚合物中结合，2和4为二维配位聚合物，3为三维配位聚合物。在配位键和离子相互作用的拓扑表示中，Ni中心表示所有四种化合物的底层（简化）网络的4-c节点。Na+、K+、Rb+和Cs+在底层网中提供配位数4,5 & 7& 8、6& 7& 8和6。大阳离子配位数高、末端水基配体数量少的化合物的周期性更高。在离子相互作用的拓扑表示中，片段{Ni(cpdc)2(H2O)2}2−扮演了底层网络的4-c（1-3）或2-c(4)节点的角色。氢键产生高度连接的三维超分子网络。用单晶x射线衍射对化合物进行了表征。直流磁数据和从头计算表明，2和3中的Ni2+离子具有正的D值和“易平面”各向异性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

The role of alkali metal cations in the construction of heterometallic NiII polymeric cyclopropane-1,1-dicarboxylates†

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The role of alkali metal cations in the construction of heterometallic NiII polymeric cyclopropane-1,1-dicarboxylates†

In this work, new Ni^II coordination compounds with cyclopropane-1,1-dicarboxylic acid (H₂cpdc) dianions were synthesized: {[Na₂Ni(cpdc)₂(H₂O)₆]·4H₂O}_n (1), {[K₆Ni₃(cpdc)₆(H₂O)₁₀]·8H₂O}_n (2), {[Rb₆Ni₃(cpdc)₆(H₂O)₁₂]·5.5H₂O}_n (3), and [Cs₂Ni(cpdc)₂(H₂O)₈]_n (4). All complexes contained mononuclear bischelate fragments {Ni^II(cpdc)₂(H₂O)₂}²⁻ bound by alkali atoms in a 1D coordination polymer for 1, 2D for 2 and 4, and 3D for 3. In the topological representation of coordination bonds and ionic interactions, the Ni center represents the 4-c node of underlying (simplified) nets for all the four compounds. Na⁺, K⁺, Rb⁺, and Cs⁺ provide coordination numbers 4, 5&7&8, 6&7&8, and 6 in the underlying nets. The periodicity is higher for compounds with higher coordination numbers of large cations and a less amount of terminal aqua ligands. In the topological representation of ionic interactions, the fragment {Ni(cpdc)₂(H₂O)₂}²⁻ plays the role of 4-c (1–3) or 2-c (4) node of the underlying nets. H-bonds produce highly connected 3D supramolecular networks. The compounds were characterized by single-crystal X-ray diffraction. The DC magnetic data and ab initio calculations revealed that Ni²⁺ ions in 2 and 3 possess a positive D value and an “easy-plane” anisotropy type.