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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The spin-states and spin-crossover behaviour of iron(II) complexes of 2,6-dipyrazol-1-ylpyrazine derivatives
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The spin-states and spin-crossover behaviour of iron(II) complexes of 2,6-dipyrazol-1-ylpyrazine derivatives

机译：2,6-二吡唑-1-基吡嗪衍生物铁（II）配合物的自旋态和自旋交叉行为

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摘要

The syntheses of[FeL_2]X_2(L=2,6-dipyrazol-1-ylpyrazine[L~2H],2,6-bis{3-methylpyrazol-l-yl} pyraxine [L~2Me],2,6-bis{3,5-dimethylpyrazol-1-yl}pyrazine [L~2Me_2] or 2,6-bis{3-[2,4,6-trimethylphenyl]pyrazol-l-yl} pyraxine [L~2Mes];X~-=BF~-_4 or ClO~-_4) are described.Solvent-free [Fe(L~2H_2)][BF_4]_2 and [Fe{L~2H)_2][ClO_4]_2 exhibit very similar abrupt spin-state transitions at 223 K and 208 K respectively,which show hysteresis loops of 3-5 K.Powder diffraction measurements afforded related,but not identical,unit cells for these two compounds,and imply that diffractionmeasurements afforded related,but not identical,unit cells for these two compounds,and imply that [Fe(L~2H)_2][ClO_4]_2 is isomorphous with [Fe(L~1H)_2][BF_4]_2 (L~1H=2,6-dipyrazol-l-ylpyridine).The signle crystalline solvate [Fe(L~2H)_2][BF_4]_2 centre dot 3CH_3NO_2 undergoes a similarly abrupt spin-state transition at 198 K.Polycrystalline [Fe(L~2Mes)_2][BF_4]_2 and [Fe(L~2Me)_2][ClO_4]_2 are isomorphous with each other and also exhibit spin-state transitions at low tmperature,although these are very different in form.In contrast,both salths of [Fe(L~2Me_2)_2]~2+ and [Fe(L~2Mes)_2]~2+ are fully low-spin at 295 K.single crystal strucutures of [Fe(L~2Me_2)_2][BF_4]_2 centre dot 0.5{CH_3}_2CO cnetre dot 0.1 H_2O and [Fe(L~2Mes)_2]~2+ are fully low-spin as a result of intra-ligand steric repulsions involving the pyrazole 5-methyl substituents.NMR and UV/vis data in MeCN and MeNO_2 show that the spin states of all four complex dications are similar in solution and the soild state except for [Fe(L~2Me_2)_2]~2+,whichexists as a mixture of high- and low-spin species in these solvents.
机译：[FeL_2] X_2（L = 2,6-dipyrazol-1-ylpyrazine [L〜2H]，2,6-bis {3-methylpyrazol-1-yl} pyraxine [L〜2Me]，2,6-的合成双{3,5-二甲基吡唑-1-基}吡嗪[L〜2Me_2]或2,6-双{3- [2,4,6-三甲基苯基]吡唑-1-基}吡嗪[L〜2Mes]; X 〜-= BF〜-_4或ClO〜-_4）。无溶剂的[Fe（L〜2H_2）] [BF_4] _2和[Fe {L〜2H）_2] [ClO_4] _2表现出非常相似的突然自旋态分别在223 K和208 K处发生跃迁，显示3-5 K的磁滞回线。粉末衍射测量提供了这两种化合物的相关但不相同的晶胞，这意味着衍射测量提供了相关但不相同的晶胞这两个化合物的分子，并暗示[Fe（L〜2H）_2] [ClO_4] _2与[Fe（L〜1H）_2] [BF_4] _2同构（L〜1H = 2,6-dipyrazol-1 -基吡啶）。单晶溶剂化物[Fe（L〜2H）_2] [BF_4] _2中心点3CH_3NO_2在198 K处经历相似的自旋态跃迁。[Fe（L〜2Mes）_2] [BF_4] _2和[Fe（L〜2Me）_2] [ClO_4] _2彼此同构并且在较低的温度下也表现出自旋态跃迁，尽管形式非常不同。相反，[Fe（L〜2Me_2）_2]〜2 +和[Fe（L〜2Mes）_2]〜2 +在295 K时完全低旋。[Fe（L〜2Me_2）_2] [BF_4] _2中心点0.5 {CH_3} _2CO中心点0.1 H_2O和[Fe（L〜2Mes）_2]〜2 +的单晶结构由于涉及吡唑5-甲基取代基的配位体内位阻而完全处于低自旋状态。MeCN和MeNO_2中的NMR和UV / vis数据表明，所有四个复合药物的自旋态在溶液和污染态下均相似[Fe（L〜2Me_2）_2]〜2 +除外，它们在这些溶剂中以高旋转种和低旋转种的混合物形式存在。

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