Vitushkina Svitlana, Potočňák Ivan, Bukrynov Oleksandr, Váhovská Lucia, Holub Mariia, Čižmár Erik
Department of Materials Physics, Institute of Experimental Physics of the Slovak Academy of Sciences, Watsonova 47, SK-040 01, Košice, Slovakia.
Department of Applied Chemistry, V. N. Karazin Kharkiv National University, Faculty of Chemistry, Svobody sq. 4, UA-61022, Kharkiv, Ukraine.
ChemistryOpen. 2025 Oct;14(10):e202500109. doi: 10.1002/open.202500109. Epub 2025 Apr 28.
Two new Cu(II) complexes with abpt (4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole) and azido ligands, [Cu(abpt)(N)]NO (1) and [Cu(abpt)(N)]⋅2HO (2), have been prepared and characterized by crystal structure analysis, spectral and magnetic measurements. The presence of neutral abpt, as well as azido ligands was proved by IR spectroscopy and the composition of the complexes confirmed an elemental analysis. Monocrystal X-ray structure analysis revealed that 1 is an ionic pentacoordinated Cu(II) complex, exhibiting a distorted tetragonal pyramidal geometry of the coordination polyhedron, while 2 is a neutral molecular complex with a distorted octahedral environment of the Cu(II) atom. The structures are stabilized by π-π stacking interactions between the aromatic rings of abpt, as well as various intra- and intermolecular hydrogen bonds involving nitrate ions and molecules of solvated water in 1 and 2, respectively. A field-induced slow magnetic relaxation was observed at low temperatures in 1, described by the direct and Raman process involving low-energy intramolecular vibrational modes, which were predicted by the DFT calculations.
已制备出两种含有4-氨基-3,5-二-2-吡啶基-4H-1,2,4-三唑（abpt）和叠氮配体的新型铜（II）配合物，即[Cu(abpt)(N₃)]NO₃ (1) 和 [Cu(abpt)(N₃)]·2H₂O (2)，并通过晶体结构分析、光谱和磁性测量对其进行了表征。通过红外光谱证实了中性abpt以及叠氮配体的存在，元素分析确定了配合物的组成。单晶X射线结构分析表明，1是一种离子型五配位铜（II）配合物，其配位多面体呈现扭曲的四方锥几何构型，而2是一种中性分子配合物，铜（II）原子处于扭曲的八面体环境中。结构通过abpt芳香环之间的π-π堆积相互作用以及分别涉及1中的硝酸根离子和2中的溶剂化水分子的各种分子内和分子间氢键得以稳定。在1中低温下观察到了场诱导的慢磁弛豫，这由涉及低能分子内振动模式的直接和拉曼过程描述，这些振动模式由密度泛函理论计算预测得出。
