β-二酮酸在类镧周围三元配位的新双核Ni-Ln配合物家族:合成、结构和磁性行为与理论支持

IF 3.4 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Biswarup Dutta, Thierry Guizouarn, Amit Gharu, Fabrice Pointillart*, Kuduva R. Vignesh* and Debashis Ray*, 
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引用次数: 0

摘要

采用双核酚醛中心不对称配体,单锅合成得到了两个新的Ni-Ln配合物系列。该方法还促进了两种类型的β-二酮酸阴离子在具有空位配位的较大镧系离子周围的封盖。以二苯甲酰甲烷(dbmH)和苯丙酮酸(bzaH)为辅助剂,得到两种不同的配合物,[NiLn(HL)2(dbm)2]NO3(其中Ln = Tb3+ (1a), Dy3+ (1b)和Ho3+ (1c))和[NiLn(HL)2(bza)2]NO3·xMeOH(其中Ln = Gd3+ (2a), x = 3;Tb3+ (2b), x = 0;Dy3+ (2c) x = 0;和Er3+ (2d), x = 0) (H2L = 2-甲氧基-6-[(E)-2 ' -羟甲基-苯氨基甲基]-苯酚),产率较高。对于配合物1a-2d,两个HL -单元首先在N2O4的细长八面体几何结构中抓住NiII离子,顶端配位为两个醇OH基团。LnIII中心随后以扭曲的O8供体为基础的方形反棱镜几何结构进行笼化。直流和交流磁化率测量表明:(1)邻近的镍(II) (S = 1)与除HoIII以外的其他镧系元素之间存在铁磁相互作用;(2)在零直流磁场中,在2k处缺乏缓慢的磁弛豫。使用从头算方法进行的计算研究涉及CASSCF(完全活动空间自一致场),rasi - so(限制活动空间状态相互作用自旋轨道),SINGLE_ANISO程序以及POLY_ANISO程序,提供了对单离子系统的磁性和弛豫机制的详细见解,特别是在镧系配合物中。理论计算支持了实验结果,即1a-1c和2b-2d在零直流场下没有缓慢的磁化弛缓,外加直流场下磁化率的异相分量没有显著的最大值。弱Ni-Ln交换和NiII和LnIII离子各向异性轴之间的非共线性导致了在所有的配合物中,即使在基态也存在显著的隧穿隙(Δtun)和基态交换耦合重态之间的QTM。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

New Family of Dinuclear Ni–Ln Complexes from Ternary Coordination by β-Diketonates around the Lanthanoids: Synthesis, Structures, and Magnetic Behavior with Theoretical Supports

New Family of Dinuclear Ni–Ln Complexes from Ternary Coordination by β-Diketonates around the Lanthanoids: Synthesis, Structures, and Magnetic Behavior with Theoretical Supports

A single-pot synthetic endeavor was utilized with a binucleating phenolate-centered unsymmetrical ligand to obtain two new series of Ni–Ln complexes. The method also facilitated the capping of two types of β-diketonate anions around larger lanthanide ions with vacant coordination sites. Using dibenzoylmethane (dbmH) and benzylacetonate (bzaH) as ancillaries, two distinct groups of complexes, [NiLn(HL)2(dbm)2]NO3 (where Ln = Tb3+ (1a), Dy3+ (1b), and Ho3+ (1c)) and [NiLn(HL)2(bza)2]NO3·xMeOH (where Ln = Gd3+ (2a), x = 3; Tb3+ (2b), x = 0; Dy3+ (2c), x = 0; and Er3+ (2d), x = 0) (H2L = 2-methoxy-6-[(E)-2′-hydroxymethyl-phenyliminomethyl]-phenol), were obtained in good yields. For complexes 1a2d, two HL units grab NiII ions first in an elongated octahedral N2O4 geometry with apical coordination of two alcohol OH groups. The LnIII centers were next caged in distorted O8 donor-based square antiprism geometry. Both dc and ac magnetic susceptibility measurements demonstrated (i) the involvement of ferromagnetic interaction between the adjacent nickel(II) (S = 1) and other lanthanoids except HoIII and (ii) a lack of slow magnetic relaxation at 2 K in zero applied dc field. The computational study using ab initio methods involving the CASSCF (Complete Active Space Self-Consistent Field), RASSI-SO (Restricted Active Space State Interaction Spin–Orbit), and SINGLE_ANISO programs, along with the POLY_ANISO program, provides detailed insights into the magnetic properties and relaxation mechanisms of single-ion systems, particularly in lanthanide complexes. Theoretical calculations backed the experimental results of the lack of slow relaxation of magnetization for 1a1c and 2b2d at zero dc field and lack of prominent maxima for the out-of-phase component of the magnetic susceptibility in the applied dc field. The weak Ni–Ln exchange and the noncollinearity between the anisotropic axes of NiII and LnIII ions led to the significant tunneling gap (Δtun) and the QTM between the ground exchange coupled doublet states in all the complexes that directed the magnetic relaxation even in the ground state.

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来源期刊
Crystal Growth & Design
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.
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