基于混合配体的两个同构配合物的晶体结构和磁性研究

doi:10.16553/j.cnki.issn1000-985x.2024.0244

摘要/Abstract

摘要： 本文以3,6-二-2-吡啶基-1,2,4,5-四嗪(DPTZ)和4,4′-氧化二苯甲酸(H₂OBA)作为双配体,分别与Co(II)离子和Cd(II)离子在溶剂热条件下反应,得到配合物[Co(OBA)(DPTZ)]·(DMF)_0.5 (1)、[Cd(OBA)(DPTZ)]·(DMF)_1.5 (2)。通过单晶X射线衍射、X射线粉末衍射、元素分析和热重分析等方法对配合物的结构进行了表征和分析,晶体结构分析表明配合物1和2同构,都属于单斜晶系,空间群为P2₁/c,每个不对称单元由1个金属离子(Co/Cd)、1个3,6-二-2-吡啶基-1,2,4,5-四嗪配体和1个4,4′-氧化二苯甲酸配体组成。每个中心金属离子(Co/Cd)具有扭曲的八面体构型,两个相邻的金属离子(Co/Cd)与羧酸配体连接,形成双核风车次级结构单元。双核风车次级结构单元与OBA配体和DPTZ配体连接构成了具有无限延展的波浪形二维层状结构。由于V型配体OBA作为柔性配体的引入,结构中形成了左手和右手的螺旋链及螺旋孔道。磁性研究结果表明,配合物1中存在反铁磁相互作用。

关键词: Co(II)配合物; Cd(II)配合物; 混合配体; 溶剂热法; 晶体结构; 磁性; 螺旋链

Abstract: 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (DPTZ) and 4,4’-oxybisbenzoic acid (H₂OBA) were used as mixed ligands to react with Co(II) ions and Cd(II) ions under solvothermal conditions, resulting in the formation of the complexes[Co(OBA)(DPTZ)]·(DMF)_0.5 (1) and [Cd(OBA)(DPTZ)]·(DMF)_1.5 (2). The structural characterization and analysis of the complexes were conducted through single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and thermogravimetric analysis. Crystallographic data reveals that complexes 1 and 2 are isostructural, belonging to the monoclinic system with the space group of P2₁/c with each asymmetric unit consisting of onemetal ion (Co/Cd), one 3,6-di(2-pyridyl)-1,2,4,5-tetrazine ligand and one 4,4’-oxybisbenzoic acid ligand. The central metal ion (Co/Cd) has a distorted octahedral configuration, and two adjacent metal ions (Co/Cd) are connected by carboxylic acid ligands, forming a dinuclear pinwheel secondary structural unit. The dinuclear pinwheel secondary structural units are connected by OBA and DPTZ ligands, resulting in an infinitely extended 2D wave-like layer. The existence of the V-shaped ligand OBA as a flexible component within the structure gives rise to both left-handed and right-handed helical chains and helical channels. Furthermore, the magnetic measurement result shows that intramolecular antiferromagnetic interaction is observed in complex 1.

Key words: Co(II) complex; Cd(II) complex; mixed ligand; solvothermal; crystal structure; magnetism; helical chain

中图分类号:

O641.4

李佳, 冯婧, 苗萌. 基于混合配体的两个同构配合物的晶体结构和磁性研究[J]. 人工晶体学报, 2025, 54(4): 693-699.

LI Jia, FENG Jing, MIAO Meng. Crystal Structure and Magnetism of Two Isomorphic Complexes Based on Mixed Ligands[J]. Journal of Synthetic Crystals, 2025, 54(4): 693-699.

参考文献

[1] OISAKI K, LI Q W, FURUKAWA H, et al. A metal-organic framework with covalently bound organometallic complexes[J]. Journal of the American Chemical Society, 2010, 132(27): 9262-9264.
[2] KITAGAWA S, KITAURA R, NORO S I. Functional porous coordination polymers[J]. Angewandte Chemie (International Edition), 2004, 43(18): 2334-2375.
[3] SONG D H, JIANG F L, YUAN D Q, et al. Optimizing sieving effect for CO₂ capture from humid air using an adaptive ultramicroporous framework[J]. Small, 2023, 19(44): e2302677.
[4] ZHENG F, CHEN R D, DING Z X, et al. Interlayer symmetry control in flexible-robust layered metal-organic frameworks for highly efficient C₂H₂/CO₂ separation[J]. Journal of the American Chemical Society, 2023, 145(36): 19903-19911.
[5] DHAKSHINAMOORTHY A, NAVALÓN S, PRIMO A, et al. Selective gas-phase hydrogenation of CO₂ to methanol catalysed by metal-organic frameworks[J]. Angewandte Chemie (International Edition), 2024, 63(3): e202311241.
[6] LI F, KAN J L, YAO B J, et al. Synthesis of chiral covalent organic frameworks via asymmetric organocatalysis for heterogeneous asymmetric catalysis[J]. Angewandte Chemie (International Edition), 2022, 61(25): e202115044.
[7] MI X N, SHENG D F, YU Y E, et al. Tunable light emission and multiresponsive luminescent sensitivities in aqueous solutions of two series of lanthanide metal-organic frameworks based on structurally related ligands[J]. ACS Applied Materials & Interfaces, 2019, 11(8): 7914-7926.
[8] DU R, WU Y F, YANG Y C, et al. Porosity engineering of MOF-based materials for electrochemical energy storage[J]. Advanced Energy Materials, 2021, 11(20): 2100154.
[9] ZHOU Y, MOORTHY S, WEI X Q, et al. A porous cobalt(ii)-organic framework exhibiting high room temperature proton conductivity and field-induced slow magnetic relaxation[J]. Dalton Transactions, 2023, 52(4): 909-918.
[10] WAN Y, ZHANG Y L, ZHANG Q, et al. Cobalt(ii) coordination polymers with single-ion magnet property[J]. CrystEngComm, 2024, 26(28): 3771-3782.
[11] WU X Q, QIN Y, YANG Z Y, et al. Construction of Co-MOF electrochemical sensor and application of it in recognizing and distinguishing naphthylamine isomers[J]. Journal of Molecular Structure, 2025, 1321: 139677.
[12] MANDAL T N, KARMAKAR A, SHARMA S, et al. Metal-organic frameworks (MOFs) as functional supramolecular architectures for anion recognition and sensing[J]. The Chemical Record, 2018, 18(2): 154-164.
[13] LIU B, ZHOU H F, HOU L, et al. Functionalization of MOFs via a mixed-ligand strategy: enhanced CO₂ uptake by pore surface modification[J]. Dalton Transactions, 2018, 47(15): 5298-5303.
[14] ABID D, MJEJRI I, JABALLI R, et al. Exploring the optical and energetic properties of a Co(II)-based mixed ligand MOF[J]. Inorganic Chemistry, 2024, 63(14): 6152-6160.
[15] TIAN Z F, YANG S Y, ZHU J L, et al. Topological and magnetic regulation in three cobalt(ii) coordination polymers constructed using a mixed bipyrimidine-tetracarboxylate strategy[J]. CrystEngComm, 2024, 26(41): 5933-5940.
[16] XU C G, LUO R, ZHANG D M, et al. Mn(II)/Co(II)-based metal-organic frameworks assembled by 5, 5′-(1, 4-xylylenediamino) diisophthalic acid and various nitrogen-containing ligands for photocatalytic and magnetic properties[J]. Journal of Solid State Chemistry, 2021, 303: 122535.
[17] ZHANG Y J, GAO L L, ZHOU W D, et al. Synthesis and magnetic properties of two Mn-based coordination polymers constructed by a mixed-ligand strategy[J]. CrystEngComm, 2020, 22(42): 7123-7128.
[18] SUN M Y, CHEN D M. A rare high-connected metal-organic framework with an unusual topological net: synthesis, crystal structure and magnetic properties[J]. Inorganic Chemistry Communications, 2017, 82: 61-63.
[19] 李波, 沈红, 王霏宇, 等. 基于混合配体的镍(Ⅱ)配合物的晶体结构、荧光性质和磁性研究[J]. 人工晶体学报, 2022, 51(11): 1952-1957.
LI B, SHEN H, WANG F Y, et al. Crystal structure, fluorescent properties and magnetism of Ni (Ⅱ) complex based on mixed ligands[J]. Journal of Synthetic Crystals, 2022, 51(11): 1952-1957 (in Chinese).
[20] ISBJAKOWA A S, GRIGORIEV M S, GOLUBEV D V, et al. Synthesis and characterization of acetylurea complexes with rare-earth metal halides: polymorphism of the praseodymium complexes[J]. Journal of Molecular Structure, 2020, 1201: 127141.

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