四氮基四核镧系配合物系列

IF 3.4 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-08-07 DOI:10.1021/acs.cgd.5c00852

Jing Xi, An-Zhi Huang, Yi-Fei Deng, Yi-Quan Zhang* and Yuan-Zhu Zhang*,

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引用次数: 0

摘要

[LnIII4(μ3-O2)2(bshHtz)2(MeOH)6(NO3)2][NO3]2·sol (Ln = Gd, 1; Tb, 2；和Dy， 3)、[DyIII4(μ3-O2)2(bshFtz)2(MeOH)2(H2O)8][DyIII4(μ3-O2)2(MeOH)2（H2O)8][NO3]4·4MeOH(4)）和[DyIII4(μ3-O2)2(MeOH)2(H2O)4（NO3)2][NO3]2·6MeOH(5)）包封了两个过氧化物阴离子，成功地合成并进行了结构和磁性表征（H2bshHtz = 3,6-bis（5-氟水杨醛肼基）-1,2,4,5-四嗪，H2bshFtz = 3,6-bis（5-甲基水杨醛肼基）-1,2,4,5-四嗪，H2bshMetz = 3,6-bis（5-甲基水杨醛肼基）-1,2,4,5-四嗪）。磁性研究表明，GdIII配合物1表现出明显的磁热效应，在7 t的磁场下，在2.5 K时，其最大值- ΔSm达到27.3 J kg-1 K - 1，并且这三种DyIII配合物均表现出典型的单分子磁铁（SMM）行为。具体来说，交流磁化率测量表明，在零直流（dc）场下，复合物3经历了单一的弛豫过程，有效能垒（Ueff）为106.5 K。相反，配合物4和5在零直流场中表现出两种明显的慢弛豫过程，配合物4的Ueff值分别为90.9 K（慢弛豫，SR）和113.3 K（快弛豫，FR），配合物5的Ueff值分别为118.4 K （SR）和73.3 K （FR）。这项工作通过在过氧化物桥接的smm中建立最高有效能垒的新记录，显着推进了LnIII过氧化物配合物领域。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Series of Tetrazine-Based Tetranuclear Lanthanide Complexes

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Series of Tetrazine-Based Tetranuclear Lanthanide Complexes

A series of centrosymmetric tetrazine-based tetranuclear lanthanide complexes with the formulas [Ln^III₄(μ₃-O₂)₂(bsh^Htz)₂(MeOH)₆(NO₃)₂][NO₃]₂·sol (Ln = Gd, 1; Tb, 2; and Dy, 3), [Dy^III₄(μ₃-O₂)₂(bsh^Ftz)₂(MeOH)₂(H₂O)₈][NO₃]₄·4MeOH (4), and [Dy^III₄(μ₃-O₂)₂(bsh^Metz)₂(MeOH)₂(H₂O)₄(NO₃)₂][NO₃]₂·6MeOH (5), encapsulating two peroxide anions, have been successfully synthesized and characterized structurally and magnetically (H₂bsh^Htz = 3,6-bis(salicylaldehydehydrazinyl)-1,2,4,5-tetrazine, H₂bsh^Ftz = 3,6-bis(5-fluorosalicylaldehydehydrazinyl)-1,2,4,5-tetrazine, and H₂bsh^Metz = 3,6-bis(5-methylsalicylaldehyde hydrazinyl)-1,2,4,5-tetrazine). Magnetic studies reveal that Gd^III complex 1 exhibits a significantly magnetocaloric effect, whose maximum −ΔS_m value reached 27.3 J kg^–1 K^–1 at 2.5 K under a magnetic field of 7 T. Furthermore, all three Dy^III complexes demonstrate typical single-molecule magnet (SMM) behavior. Specifically, alternating-current susceptibility measurements indicate that complex 3 experiences a single relaxation process under a zero direct-current (dc) field, with an effective energy barrier (U_eff) of 106.5 K. In contrast, complexes 4 and 5 exhibit two distinct slow relaxation processes of magnetization in a zero dc field, with U_eff values of 90.9 K (slow relaxation, SR) and 113.3 K (fast relaxation, FR) for complex 4 and 118.4 K (SR) and 73.3 K (FR) for complex 5, respectively. This work significantly advances the field of Ln^III peroxide complexes by establishing a new record for the highest effective energy barrier reported among peroxide-bridged SMMs.

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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.