Structural dynamics of a thermally silent triiron(II) spin crossover defect grid complex.
Structural dynamics of a thermally silent triiron(II) spin crossover defect grid complex.
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DOI：
10.1039/d3dt02067c
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发表时间：
2023-09-13
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需要了解自旋交叉(SCO)络合物在平衡和非平衡条件下的自旋跃迁过程中的结构演变，以使它们能够成功地应用于显示器、致动器和存储元件。用衍射法研究了[Fe3LH2(HLh)2](BF4)4·4MeCN(Fe3)，Lh=3，5-双{6-(2，2‘-联吡啶)}吡唑[2×2]三铁(II)缺陷金属的结构随温度升高和光照的变化。虽然对单晶的多温度结晶学研究证明该化合物没有表现出热自旋转变，但对缺陷网格的结构分析表明，由没有金属的顶点提供的网格的灵活性导致了有趣的特征，可用于相关热响应系统中的分子间协同作用。时间分辨光结晶学结果表明，在ps激光脉冲激发下，缺陷网格显示了失稳过程的前两个步骤，即分别发生在ps和ns时间尺度上的光致和弹性步骤。与以前报道的[2×2]四铁(II)金属栅格类似，Fe3在光致步骤中表现出整个晶格的局部变形，而在弹性步骤中表现出晶格的长程变形。尽管纯光致高自旋(HS)态在四核晶格中的寿命比在缺陷晶格中的长，这表明全局核度对光生物种的寿命起着至关重要的作用，但共晶溶剂对光致高自旋(HS)态寿命的影响尚不清楚。这一研究揭示了一种热沉默缺陷三铁系金属栅的失稳动力学。研究了一种三铁(II)金属格栅在升温和光照条件下的性能。在缺乏热自旋转变的情况下，时间分辨光晶学揭示了非平衡动力学的光诱导和弹性步骤。
The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to study the structural changes accompanying the temperature increase and the light irradiation of a defect [2 × 2] triiron(ii) metallogrid of the form [FeII3LH2(HLH)2](BF4)4·4MeCN (FE3), LH = 3,5-bis{6-(2,2′-bipyridyl)}pyrazole. Although a multi-temperature crystallographic investigation on single crystals evidenced that the compound does not exhibit a thermal spin transition, the structural analysis of the defect grid suggests that the flexibility of the grid, provided by a metal-devoid vertex, leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. Time-resolved photocrystallography results reveal that upon excitation with a ps laser pulse, the defect grid shows the first two steps of the out-of-equilibrium process, namely the photoinduced and elastic steps, occurring at the ps and ns time scales, respectively. Similar to a previously reported [2 × 2] tetrairon(ii) metallogrid, FE3 exhibits a local distortion of the entire grid during the photoinduced step and a long-range distortion of the lattice during the elastic step. Although the lifetime of the pure photoinduced high spin (HS) state is longer in the tetranuclear grid than in the defect grid, suggesting that the global nuclearity plays a crucial role for the lifetime of the photoinduced species, the influence of the co-crystalising solvent on the lifetime of the photoinduced HS state remains unknown. This study sheds light on the out-of-equilibrium dynamics of a thermally silent defect triiron SCO metallogrid. A triiron(II) metallogrid was studied upon temperature increase and light irradiation. While lacking thermal spin transition, time-resolved photocrystallography revealed the photoinduced and elastic steps of the out-of-equilibrium dynamics.
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