Cu(II) Complexes with Fluoroalkyl-Pyrazolyl-Substituted Nitronyl Nitroxides

IF 3.6 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-09-22 DOI:10.1021/acs.cgd.6c01128

Galina Romanenko, Natalia Artiukhova, Sergey Fokin, Evgeny Tretyakov, Bogdan Ugrak, Kristina Aidakova, Gleb Letyagin, Artem Bogomyakov

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引用次数: 0

Abstract

Synthetic methods of heterospin compounds based on copper hexafluoroacetylacetonate [Cu(hfac)₂] and nitronyl nitroxide radicals containing fluorinated alkyl substituents in the pyrazole ring 2-(1-R-3-pyrazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl, where R = CHF₂ (L¹²), CH₂CH₂F (L²¹), CH₂CHF₂ (L²²) or CH₂CF₃ (L²³) were developed. Single crystals of two chain polymers [Cu(hfac)₂(L¹²)]_n and [Cu(hfac)₂L²³]_n·0.5C₆H₁₄ and solvates of molecular [Cu₃(hfac)₆(L²¹)₂]·C₆H₁₄, [Cu₃(hfac)₆(L²²)₂]·2CH₂Cl₂, [Cu₅(hfac)₁₀(L²¹)₄]·solv (solv = C₆H₁₄, 2CH₂Cl₂) and [Cu₅(hfac)₁₀(L²²)₄]·C₆H₁₄ complexes were grown. Their structures and magnetic properties were studied. It was established that upon cooling of the [Cu₅(hfac)₁₀(L²¹)₄]·2CH₂Cl₂ crystal, a magneto-structural phase transition associated with a reduction in the Cu−O_NO distances in the environment of the central Cu atom is realized. The transformation of this three-spin exchange cluster {>N−O^•−Cu(II)−^•O−N<} leads to a change in the nature of the exchange interactions from ferro-to antiferromagnetic, which is reflected in the type of temperature dependence of the effective magnetic moment.

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含氟烷基吡唑取代硝基氮氧化物的Cu（II）配合物

以六氟乙酰丙酮铜[Cu(hfac)2]和硝基氮氧化物自由基为基础合成吡唑环2-（1-R-3-吡唑-4-基）-4,4,5,5-四甲基-2-咪唑-3-氧化物-1-氧基含氟取代基的异旋化合物，其中R = CHF2 （L12）、CH2CH2F （L21）、CH2CHF2 （L22）或CH2CF3 （L23）。生长了两种链式聚合物[Cu(hfac)2(L12)]n和[Cu(hfac)2L23]n·0.5 5c6h14的单晶和[Cu3(hfac)6(L21)2]·C6H14、[Cu3(hfac)6(L22)2]·2CH2Cl2、[Cu5(hfac)10(L21)4]·solv （solv = C6H14, 2CH2Cl2）和[Cu5(hfac)10(L22)4]·C6H14配合物的溶剂化物。研究了它们的结构和磁性能。结果表明，在[Cu5(hfac)10(L21)4]·2CH2Cl2晶体冷却后，在中心Cu原子环境中发生了与Cu−ONO距离减小相关的磁结构相变。三自旋交换簇{>；N−O•−Cu(II)−O−N<；}的转变导致交换相互作用的性质从铁磁转变为反铁磁，这反映在有效磁矩的温度依赖类型上。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.