Razquin-Bobillo Laura, Pajuelo-Corral Oier, Zabala-Lekuona Andoni, Rodríguez-Diéguez Antonio, Cepeda Javier
Departamento de Química Aplicada, Facultad de Química, Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU), 20018 Donostia-San Sebastián, Spain.
Departamento de Química Inorgánica, UEQ, Universidad de Granada, C/ Severo Ochoa s/n, 18071, Granada, Spain.
Dalton Trans. 2022 Nov 1;51(42):16243-16255. doi: 10.1039/d2dt02401b.
Two new isostructural compounds based on 6-methyl-2-oxonicotinate (6m2onic) ligand and sodium and lanthanide(III) ions are reported. The structural and chemical characterization reveals the following chemical formula: {[Ln(6m2onic)(μ-6m2onic)Na(HO)]·8HO} [where Ln(III) = Dy (1Dy) and Er (2Er)]. These compounds crystallize in the form of one-dimensional arrays held together into a hydrogen-bonded structure, in which 6m2onic ligands establish four ,' chelating rings with the lanthanide to render a distorted square antiprism (SAPR) geometry. Magnetic dc and ac susceptibility measurements confirm that 1Dy and 2Er behave as SIMs. Magnetic dilutions using Y(III) matrices have been made to achieve a Dy(III) counterpart (1Y/Dy) that presents slow magnetic relaxation under zero dc field. Under an optimized field (of 1000 Oe and 1500 Oe for 1Y/Dy and 2Y/Er, respectively), 1Y/Dy reveals the occurrence of two well-separated maxima, attributed to SR ( = 65.2 K (45.3 cm) and = 2.76 × 10 s) and FR processes ( = 23.2 K (16.1 cm) and = 1.40 × 10 s), whereas 2Y/Er shows a multiple relaxation pathway that considers quantum tunnelling of the magnetization (QTM), Orbach, Raman and direct mechanisms. calculations have been carried out to support the experimental evidence and to explain the lanthanide ion-dependent behaviour deepen the understanding of the magneto-structural relationship of the SAPR environment.
报道了两种基于6-甲基-2-氧代烟酸酯(6m2onic)配体以及钠和镧系(III)离子的新的同构化合物。结构和化学表征揭示了以下化学式:{[Ln(6m2onic)(μ-6m2onic)Na(HO)]·8HO} [其中Ln(III) = Dy (1Dy) 和 Er (2Er)]。这些化合物以一维阵列的形式结晶,通过氢键结构结合在一起,其中6m2onic配体与镧系元素形成四个螯合环,呈现出扭曲的四方反棱柱(SAPR)几何形状。直流和交流磁化率测量证实1Dy和2Er表现为单离子磁体。使用Y(III)基质进行了磁稀释,以获得在零直流场下呈现缓慢磁弛豫的Dy(III)对应物(1Y/Dy)。在优化场(1Y/Dy和2Y/Er分别为1000 Oe和1500 Oe)下,1Y/Dy显示出两个明显分开的最大值,分别归因于慢弛豫( = 65.2 K (45.3 cm) 和 = 2.76 × 10 s)和快弛豫过程( = 23.2 K (16.1 cm) 和 = 1.40 × 10 s),而2Y/Er显示出考虑磁化量子隧穿(QTM)、奥尔巴赫、拉曼和直接机制的多重弛豫途径。已经进行了计算以支持实验证据并解释镧系离子依赖性行为,加深了对SAPR环境磁结构关系的理解。