Cooperative Spin-Crossover in a Neutral Dinuclear Complex Based on a Functionalized Triazole Ligand

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-03-26 DOI:10.1021/acs.cgd.5c0015810.1021/acs.cgd.5c00158

Thirunavukkarasu Thangavel, Nour-el-Islam Belmouri, Catherine Charles, Ahmad Hobballah, Longhe Li, Carlos J. Gómez-García, Sébastien Pillet, Kamel Boukheddaden* and Smail Triki*,

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Abstract

A novel spin-crossover (SCO) dinuclear complex, [Fe₂(μ₂-cp-trz)₃(cp-trz)₂(tcm)₄] (cp-trz = 4-cyclo-pentyl-1,2,4-triazole, tcm- = tricyanomethanide anion), was synthesized and thoroughly characterized. Crystallographic analyses at 250 and 180 K revealed a centrosymmetric dinuclear structure with Fe(II) centers bridged by triazole ligands. The complex exhibits a cooperative hysteretic thermally induced abrupt one-step spin transition between high-spin (HS) and low-spin (LS) states. Magnetic measurements (Magn), X-rays diffraction (XRD), and optical microscopy (OM) show the following switching temperatures: T_1/2↓^Magn = 202 K and T_1/2↑^Magn = 212 K, and T_1/2↓^OM ≃ T_1/2↓^XRD = 203 K and T_1/2↑^OM ≃ T_1/2↑^XRD = 207 K. Moreover, structural and OM studies reveal significant anisotropic lattice changes, driven by strong hydrogen bonding along the c axis, which underpins the cooperative behavior of the SCO transition, and propagation of the HS/LS interface along the spin transition.

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基于功能化三唑配体的中性双核配合物的协同自旋交叉

合成了一种新型自旋交叉（SCO）双核配合物[Fe2(μ2-cp-trz)3(cp-trz)2(tcm)4] （cp-trz = 4-环戊基-1,2,4-三唑，tcm- =三氰甲烷阴离子），并对其进行了表征。在250和180 K下的晶体学分析显示了一个中心对称的双核结构，铁（II）中心由三唑配体桥接。该配合物在高自旋态（HS）和低自旋态（LS）之间表现出热诱导的协同滞后单步自旋跃迁。磁测量（Magn）、x射线衍射（XRD）和光学显微镜（OM）结果表明：T1/2↓Magn = 202 K和T1/2↑Magn = 212 K, T1/2↓OM≠T1/2↓XRD = 203 K和T1/2↑OM≠207 K。此外，结构和OM研究揭示了显著的各向异性晶格变化，这是由沿c轴的强氢键驱动的，这支撑了SCO跃迁的合作行为，以及HS/LS界面沿自旋跃迁的传播。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.