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An Incomplete Spin Transition Associated with a Z′=1→Z′=24 Crystallographic Symmetry Breaking

机译:Z= 1→Z= 24晶体对称性破坏相关的不完全自旋跃迁

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摘要

Crystalline [FeL 2][BF4]2 >⋅Me2CO (L=N‐[2,6‐di{pyrazol‐1‐yl}pyrid‐4‐yl]acetamide) is high‐spin at room temperature, and undergoes an abrupt, hysteretic spin‐crossover at T 1/2 =137 K (ΔT 1/2 =14 K) that proceeds to about 50 % completeness. This is associated with a crystallographic phase transition, from phase 1 (P21/c, Z=4) to phase 2 (P21, Z=48). The cations associate into chains in the crystal through weak intermolecular π⋅⋅⋅π interactions. Phase 2 contains a mixture of high‐spin and low‐spin molecules, which are grouped into triads along these chains. The perchlorate salt [FeL 2][ClO4]2 >⋅Me2CO also adopts phase 1 at room temperature but undergoes a different phase transition near 135 K to phase 3 (P21/c, Z=8) without a change in spin state.
机译:结晶[FeL 2] [BF4] 2 >⋅ Me2CO(L = N- [2,6-二二{吡唑-1-基}吡啶-4-基]乙酰胺)在室温下高旋转温度,并在T 1/2 = 137 K(ΔT1/2 = 14 K)处发生突然的磁滞自旋交叉,直至完成约50%。这与从相1(P21 / c,Z = 4)到相2(P21,Z = 48)的晶体学相变有关。阳离子通过微弱的分子间π⋅⋅⋅π相互作用缔合成晶体中的链。 2相包含高自旋和低自旋分子的混合物,它们沿着这些链分为三联体。高氯酸盐[FeL 2] [ClO4] 2 >⋅ Me2CO在室温下也采用1相,但在135 K附近转变为3相(P21 / c,Z = 8)而没有相变。旋转状态改变。

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