Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL _3](ClO _4) _2

Thompson J.R.; Archer R.J.; Hawes C.S.; Ferguson A.; Wattiaux A.; Mathonière C.; Clérac R.; Kruger P.E.

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Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL _3](ClO _4) _2

机译：Fe（ii）咪唑基亚胺复合物：[FeL _3]（ClO _4）_2的热和光诱导自旋交叉行为

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Herein we report the synthesis, structure and magnetic properties of [FeL _3](ClO _4) _2, 1, where L is the bidentate ligand N-(4-methoxyphenyl)-1H-imidazol-2-yl-methanimine. Complex 1 crystallises as the mer-isomer which is stabilised by intramolecular π-π interactions between the methoxyphenyl 'tail' and imidazole 'head' of adjacent ligands centred around Fe(ii). The crystal lattice is devoid of any significant intermolecular π-π interactions between neighbouring complexes, although hydrogen bonding between two imidazole N-H groups and two perchlorate anions links two adjacent complexes together and allows them to buttress up against one another. Structural data collected at 116 and 292 K suggest a spin-crossover (SCO) behaviour for 1 as Fe-N bond lengths increase by ca. 10% at the higher temperature. SCO behaviour is confirmed by magnetic susceptibility measurements. The χT vs. T data reveals a complete and reversible SCO for 1 with T _(1/2) of 158 K, and this is further confirmed by M?ssbauer spectroscopy (at 4.2 and 293 K) and variable temperature reflectivity measurements. Indeed, upon irradiation with red light (647 nm) at 10 K, 1 shows a photo-induced spin-crossover and undergoes full switching between the LS and HS states.

机译：本文中，我们报道了[FeL _3]（ClO _4）_2，1的合成，结构和磁性能，其中L是双齿配体N-（4-甲氧基苯基）-1H-咪唑-2-基-甲基亚胺。配合物1结晶为美体异构体，并通过以Fe（ii）为中心的相邻配体的甲氧基苯基“尾”与咪唑“头”之间的分子内π-π相互作用而稳定。尽管两个咪唑N-H基团和两个高氯酸根阴离子之间的氢键将两个相邻的络合物连接在一起并使它们彼此抵靠，但晶格中没有任何明显的分子间π-π相互作用。在116和292 K处收集到的结构数据表明，随着Fe-N键长度增加约1，自旋交叉（SCO）行为为1。在较高温度下为10％。 SCO行为通过磁化率测量得到证实。 χT与T的数据揭示了T_（1/2）为158 K的1的完全可逆SCO，这由Msssbauer光谱法（分别在4.2和293 K下）和可变温度反射率测量进一步证实。实际上，在10 K的红光（647 nm）照射下，1显示出光诱导的自旋交叉，并且在LS和HS状态之间进行了完全切换。

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《Dalton transactions: An international journal of inorganic chemistry》 |2012年第41期|共6页
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Thompson J.R.; Archer R.J.; Hawes C.S.; Ferguson A.; Wattiaux A.; Mathonière C.; Clérac R.; Kruger P.E.;
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Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL _3](ClO _4) _2

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